Recycled ABS modified material and preparation method thereof

Abstract

The invention provides a recycled ABS (Acrylonitrile Butadiene Styrene) modified material and a preparation method thereof, and belongs to the technical field of waste plastic modification. According to the recycled ABS modified material provided by the invention, common waste ABS plastic is taken as a raw material and is subjected to melt blending with the unsaturated anhydride compound, the unsaturated rubber and the initiator, so that the environmental problem caused by waste ABS plastic is effectively solved, and a certain economic value can be created. Compared with recycled waste ABS plastic, the recycled ABS modified material provided by the invention has the advantages that the mechanical property is obviously improved, and particularly, the toughness is obviously improved. The modification processing method provided by the invention has the advantages of low technical requirements, same equipment requirements as common polymer extrusion processing, small investment and high product economic value, and is suitable for industrial production and market popularization and application.

Description

Technical Field

[0001] The invention belongs to the technical field of waste plastic modification, and particularly relates to a recycled ABS modified material and a preparation method thereof. Background Art

[0002] In 2021, China's ABS resin production was about 4.3083 million tons, a year-on-year increase of 7.8%. With the increasing use of resin, the problem of waste plastic disposal has also been brought about. Waste plastics are generally disposed of by landfill or incineration, but these treatment methods not only cause environmental pollution, but also cause huge waste. Such a large number of waste plastics has brought great harm to our living environment and physical and mental health, so that the recycling of waste plastics has attracted widespread attention from the academic community. If waste plastics can be modified to improve the performance of waste plastics and achieve their high-value reuse, it will not only solve the problem of waste plastic disposal but also generate new economic value.

[0003] The prior art discloses a variety of ABS recycled material recycling and modification technologies. For example, Chinese patent document No. 201610541118.4 discloses a method for modifying waste ABS materials. The processing process is also extrusion processing. Two compounds, bisoxazoline and acid anhydride, are added to the modified formula of waste ABS materials. Although the modified ABS material has good mechanical properties, there is still room for improvement. Summary of the invention

[0004] In view of this, the technical problem to be solved by the present invention is to provide a recycled ABS modified material and a preparation method thereof. The mechanical properties of the material obtained by the present invention are greatly improved and can be processed and applied again.

[0005] According to one aspect of the present invention, there is provided a recycled ABS modified material, which is prepared by melt blending raw materials, wherein the raw materials contain, by mass, 100 parts of recycled ABS material, 0.5 to 5 parts of unsaturated anhydride compounds, 5 to 30 parts of unsaturated rubber, and 0.2 to 2 parts of initiator.

[0006] Optionally, the raw materials contain, by mass, 100 parts of recycled ABS material, 1 to 3 parts of unsaturated acid anhydride compounds, 5 to 20 parts of unsaturated rubber, and 0.5 to 1.5 parts of initiator.

[0007] Optionally, the unsaturated acid anhydride compound is selected from at least one of maleic anhydride, itaconic anhydride or acrylic anhydride.

[0008] Optionally, the unsaturated rubber is selected from at least one of styrene-butadiene rubber, nitrile-butadiene rubber or polybutadiene rubber.

[0009] Optionally, the initiator is an organic peroxide initiator or a high temperature resistant initiator.

[0010] Optionally, the organic peroxide initiator is selected from at least one of dicumyl peroxide and benzoyl peroxide.

[0011] Optionally, the high temperature resistant initiator is selected from at least one of 2,3-dimethyl-2,3-diphenyl-butane and 2,3-diethyl-2,3-diphenyl-pentane.

[0012] The present invention prepares a recycled ABS modified material with excellent mechanical properties by melt blending recycled ABS material, unsaturated acid anhydride compound, unsaturated rubber and initiator, so that the mechanical properties of the recycled ABS material are greatly improved. Taking general recycled ABS material as an example, the tensile strength of ABS before melt blending is lower than 35MPa, the bending strength is lower than 56Mpa, and the notched impact strength is lower than 5.7kJ / m 2 ; The tensile strength of the modified ABS plastic after melt blending is ≥48MPa, the bending strength is ≥64MPa, and the impact strength is ≥12.0kJ / m 2 .

[0013] In the present invention, the tensile strength is tested according to the standard test method GB / T1040-92; the flexural strength is tested according to the standard test method GB / T 9341-2000; and the notched impact strength is tested according to the standard test method GB1843-80.

[0014] According to another aspect of the present invention, there is provided a method for preparing a recycled ABS modified material, comprising the following steps:

[0015] a) subjecting a mixture I containing recycled ABS material and unsaturated anhydride compounds to melt blending I and forming and curing I to obtain an intermediate modified with the unsaturated anhydride compounds;

[0016] b) melt blending II, molding and curing II the mixture II containing the intermediate, unsaturated rubber and initiator.

[0017] Optionally, the ratio of the recycled ABS material to the unsaturated anhydride compound, the unsaturated rubber and the initiator is 100:0.5-5:5-30:0.2-2 in parts by mass.

[0018] Optionally, the unsaturated acid anhydride compound is selected from at least one of maleic anhydride, itaconic anhydride or acrylic anhydride.

[0019] Optionally, the unsaturated rubber is selected from at least one of styrene-butadiene rubber, nitrile-butadiene rubber or polybutadiene rubber.

[0020] Optionally, the initiator is selected from at least one of dicumyl peroxide, benzoyl peroxide, 2,3-dimethyl-2,3-diphenyl-butane or 2,3-diethyl-2,3-diphenyl-pentane.

[0021] Optionally, the temperature of the melt blending I is 200-220°C.

[0022] Optionally, after obtaining the intermediate, it is dried at 70-90° C. for 8-12 hours.

[0023] Optionally, the temperature of the melt blending II is 180-200°C.

[0024] Optionally, in the step a), the recycled ABS material is crushed and sieved to obtain flakes, and the maximum size of the flakes does not exceed 10 mm.

[0025] Optionally, after obtaining the flake material, it is dried at 70-90° C. for 8-12 hours.

[0026] According to another aspect of the present invention, there is provided a recycled ABS modified material prepared by the above preparation method.

[0027] Optionally, the tensile strength of the recycled ABS modified material is ≥48MPa, and / or the flexural strength is ≥64MPa, and / or the impact strength is ≥12.0kJ / m 2 .

[0028] The present invention has the following beneficial effects:

[0029] The present invention uses a melt blending processing method to process general waste ABS materials, effectively solving the environmental problems caused by waste ABS plastics, and can also create certain economic value. The mechanical properties of the recycled ABS modified material provided by the present invention are significantly improved compared with the recycled waste ABS plastics, especially the toughness is significantly improved, the tensile strength is ≥48MPa, the bending strength is ≥64MPa, and the impact strength is ≥12.0kJ / m 2 , the tensile strength is increased by at least 37.1%, the bending strength is increased by at least 14.3%, and the impact strength is increased by at least 110.5%. The modification processing method provided by the present invention has low technical requirements and a simple processing method; low equipment requirements, which are the same as general polymer extrusion processing; small investment, high product economic value, and is suitable for industrial production and market promotion and application. DETAILED DESCRIPTION

[0030] The present invention will be further described in detail below by way of examples, which are merely illustrative and are not intended to limit the scope of application of the present invention. The raw materials or components used in the present invention can be obtained by commercial routes or conventional methods unless otherwise specified.

[0031] The recycled ABS modified material provided by the invention is prepared by melt blending recycled ABS material, unsaturated acid anhydride compound, unsaturated rubber and initiator.

[0032] The recycled ABS material used in the present invention can be directly obtained from recycled ABS plastic products.

[0033] In an embodiment of the present invention, the tensile strength of the recycled ABS material is lower than 35 MPa.

[0034] In an embodiment of the present invention, the flexural strength of the recycled ABS material is lower than 56 MPa.

[0035] In the embodiment of the present invention, the notched impact strength of the recycled ABS material is lower than 5.7 kJ / m 2 .

[0036] In the present invention, the unsaturated acid anhydride compound is a mixture of one or more of maleic anhydride, itaconic anhydride or acrylic anhydride in any proportion. The unsaturated rubber is a mixture of one or more of styrene-butadiene rubber, nitrile rubber or polybutadiene rubber in any proportion. The initiator is a mixture of one or more of dicumyl peroxide, benzoyl peroxide, 2,3-dimethyl-2,3-diphenyl-butane or 2,3-diethyl-2,3-diphenyl-pentane in any proportion.

[0037] In the raw materials, by weight, the recycled ABS material is 100 parts; the unsaturated anhydride compound is 0.5-5 parts, preferably 1-3 parts; the unsaturated rubber is 5-30 parts, preferably 5-20 parts; the initiator is 0.2-2 parts, preferably 0.5-1.5 parts.

[0038] The recycled ABS modified material provided by the present invention has a tensile strength of ≥48MPa, a flexural strength of ≥64MPa, and an impact strength of ≥12.0kJ / m 2 The tensile strength is increased by at least 37.1%, the flexural strength is increased by at least 14.3%, and the impact strength is increased by at least 110.5%, and the mechanical properties are good.

[0039] The specific process of preparing and recycling the ABS modified material provided by the present invention is:

[0040] a) recovering the ABS material and melt-blending it with an unsaturated acid anhydride compound to obtain an intermediate modified by the unsaturated acid anhydride compound;

[0041] b) The intermediate modified by the unsaturated acid anhydride compound is melt-blended with the unsaturated rubber and the initiator to obtain the recycled ABS modified material.

[0042] In the above technical solution, the recycled ABS material needs to be crushed before step a), and the recycled ABS material is crushed by a crusher and filtered by a screen to obtain fine flakes, and the maximum size of the flakes does not exceed 10 mm.

[0043] Preferably, the flaky recovered ABS material after crushing and filtration is dried in a forced air oven at 70 to 90° C. for 8 to 12 hours.

[0044] In the above technical solution, the temperature of the melt blending in step a) is 200-220°C. The present invention does not particularly limit the equipment used for the melt blending, and a twin-screw extruder is preferably used. In the present invention, the temperature of each section of the twin-screw extruder from the hopper to the die during the melt blending process is preferably 200°C, 205°C, 210°C, 215°C, 220°C, 215°C, 210°C, and 210°C, respectively.

[0045] After the melt blending in step a) is completed, the melt is cooled and granulated in sequence to obtain an intermediate ABS material.

[0046] Preferably, the intermediate ABS material modified by the unsaturated anhydride compound is dried in a forced air oven at 70 to 90° C. for 8 to 12 hours.

[0047] In the above technical solution, the temperature of the melt blending in step b) is 180-200°C. The present invention does not particularly limit the equipment used for the melt blending, and preferably a twin-screw extruder. In the present invention, the temperatures of the twin-screw extruder from the hopper to the die during the melt blending are preferably 180°C, 180°C, 185°C, 190°C, 195°C, 200°C, 195°C, and 190°C, respectively.

[0048] After the melt blending in step b) is completed, the melt is cooled and granulated in sequence to obtain the final recycled ABS modified material.

[0049] The processing method provided by the invention can obtain recycled modified ABS material with excellent mechanical properties, so that waste ABS plastics can be effectively reused, the impact on the environment can be reduced, and good economic and social benefits can be brought about.

[0050] In the embodiment of the present invention, the twin-screw extruder used is a KET-36A extruder produced by Kolter Company.

[0051] In the embodiment of the present invention, the recycled ABS material comes from Dongguan Xinyixin Plastic Co., Ltd.;

[0052] Nitrile rubber and polybutadiene rubber are from Dongguan Xinrui New Materials Co., Ltd.

[0053] Maleic anhydride, itaconic anhydride, acrylic anhydride, and 2,3-dimethyl-2,3-diphenyl-butane were from MacLean;

[0054] Dicumyl peroxide and benzoyl peroxide were from Sigma-Aldrich.

[0055] Example 1

[0056] The flakes with a maximum size of no more than 10 mm obtained after crushing the recycled ABS material were placed in a forced air drying oven and dried at 80° C. for 8 h.

[0057] 1000g of the flake material of the recycled ABS material and 15g of maleic anhydride were mixed evenly, and then added to a twin-screw extruder for melt blending. The temperature of each section from the hopper to the die of the twin-screw extruder was set to 200°C, 205°C, 210°C, 215°C, 220°C, 215°C, 210°C, and 210°C. After the melt blending, the material was cooled and granulated to obtain an intermediate ABS material modified by unsaturated anhydride compounds.

[0058] The intermediate ABS material was placed in a forced air oven at 80° C. and dried for 8 h.

[0059] The dried intermediate ABS material, 100 g of polybutadiene rubber and 12 g of dicumyl peroxide were mixed uniformly and then added to a twin-screw extruder for melt blending. The temperatures of each section from the hopper to the die of the twin-screw extruder were set to 180° C., 180° C., 185° C., 190° C., 195° C., 200° C., 195° C. and 190° C. After the melt blending, the material was cooled and granulated to obtain a recycled ABS modified material.

[0060] Example 2

[0061] The flakes with a maximum size of no more than 10 mm obtained after crushing the recycled ABS material were placed in a forced air drying oven and dried at 80° C. for 8 h.

[0062] 1000g of the flake material of the recycled ABS material and 1g of maleic anhydride were mixed evenly, and then added to a twin-screw extruder for melt blending. The temperature of each section from the hopper to the die of the twin-screw extruder was set to 200°C, 205°C, 210°C, 215°C, 220°C, 215°C, 210°C, and 210°C. After the melt blending, the material was cooled and granulated to obtain an intermediate ABS material modified by unsaturated anhydride compounds.

[0063] The intermediate ABS material was placed in a forced air oven at 80° C. and dried for 8 h.

[0064] The dried intermediate ABS material, 100 g of polybutadiene rubber and 12 g of dicumyl peroxide were mixed uniformly and then added to a twin-screw extruder for melt blending. The temperatures of each section from the hopper to the die of the twin-screw extruder were set to 180° C., 180° C., 185° C., 190° C., 195° C., 200° C., 195° C. and 190° C. After the melt blending, the material was cooled and granulated to obtain a recycled ABS modified material.

[0065] Example 3

[0066] The flakes with a maximum size of no more than 10 mm obtained after crushing the recycled ABS material were placed in a forced air drying oven and dried at 80° C. for 8 h.

[0067] 1000g of recycled ABS flakes and 7g of acrylic anhydride were mixed evenly and added to a twin-screw extruder for melt blending. The temperature of each section from the hopper to the die of the twin-screw extruder was set to 200°C, 205°C, 210°C, 215°C, 220°C, 215°C, 210°C, and 210°C. After the melt blending, the mixture was cooled and granulated to obtain an intermediate ABS material modified by unsaturated anhydride compounds.

[0068] The intermediate ABS material was placed in a forced air oven at 80° C. and dried for 8 h.

[0069] The dried intermediate ABS material, 100 g of polybutadiene rubber, and 12 g of 2,3-dimethyl-2,3-diphenylbutane were uniformly mixed and added to a twin-screw extruder for melt blending. The temperatures of each section from the hopper to the die of the twin-screw extruder were set to 180° C., 180° C., 185° C., 190° C., 195° C., 200° C., 195° C., and 190° C. After the melt blending, the material was cooled and granulated to obtain a recycled ABS modified material.

[0070] Example 4

[0071] The flakes with a maximum size of no more than 10 mm obtained after crushing the recycled ABS material were placed in a forced air drying oven and dried at 80° C. for 8 h.

[0072] 1000g of the flake material of the recycled ABS material and 15g of itaconic anhydride were mixed evenly, and then added to a twin-screw extruder for melt blending. The temperature of each section from the hopper to the die of the twin-screw extruder was set to 200°C, 205°C, 210°C, 215°C, 220°C, 215°C, 210°C, and 210°C. After the melt blending, the material was cooled and granulated to obtain an intermediate ABS material modified by unsaturated anhydride compounds.

[0073] The intermediate ABS material was placed in a forced air oven at 80° C. and dried for 8 h.

[0074] The dried intermediate ABS material, 100 g of nitrile rubber and 15 g of benzoyl peroxide were uniformly mixed and added to a twin-screw extruder for melt blending. The temperatures of each section from the hopper to the die of the twin-screw extruder were set to 180° C., 180° C., 185° C., 190° C., 195° C., 200° C., 195° C. and 190° C. After the melt blending, the material was cooled and granulated to obtain a recycled ABS modified material.

[0075] Comparative Example 1

[0076] The preparation of the recycled ABS modified material is similar to that in Example 3, except that 2,3-dimethyl-2,3-diphenylbutane is not added to the formula.

[0077] Comparative Example 2

[0078] The preparation of the recycled ABS modified material is similar to that in Example 3, except that no acrylic anhydride is added to the formulation.

[0079] Comparative Example 3

[0080] The preparation of the recycled ABS modified material was similar to that in Example 4, except that 500 g of nitrile rubber was added to the formula.

[0081] The tensile strength, flexural strength and notched impact strength of the recycled ABS modified materials obtained in Example 1, Example 2, Example 3 and Example 4 and Comparative Examples 1 to 3 were tested. The tensile strength was tested according to the standard test method GB / T1040-92; the flexural strength was tested according to the standard test method GB / T 9341-2000; and the notched impact strength was tested according to the standard test method GB1843-80.

[0082] The test results are shown in Table 1.

[0083] Table 1 Mechanical properties test results of recycled modified ABS materials

[0084]

[0085]

[0086] It can be seen from Table 1 that the mechanical properties of the recycled modified ABS plastic provided by the present invention are significantly better than those of the recycled ABS material.

[0087] Any numerical value mentioned in the present invention includes all values ​​that increase by one unit each time from the lowest value to the highest value if there is only an interval of two units between any minimum value and any maximum value. For example, if the amount of a component, or the value of a process variable such as temperature, pressure, time, etc. is declared to be 50-90, in this specification it means that 51-89, 52-88... and 69-71 and 70-71 are specifically listed. For non-integer values, 0.1, 0.01, 0.001 or 0.0001 can be appropriately considered as a unit. These are just some specially specified examples. In this application, in a similar manner, all possible combinations of numerical values ​​between the listed lowest and highest values ​​are considered to have been disclosed.

[0088] It should be noted that the embodiments described above are only used to explain the present invention and do not constitute any limitation to the present invention. The present invention has been described with reference to typical embodiments, but it should be understood that the words used therein are descriptive and explanatory words, rather than restrictive words. The present invention may be modified as specified within the scope of the claims of the present invention, and the present invention may be revised without departing from the scope and spirit of the present invention. Although the present invention described therein relates to specific methods, materials and embodiments, it does not mean that the present invention is limited to the specific examples disclosed therein, on the contrary, the present invention can be extended to all other methods and applications with the same functions.

Claims

1. A method for recycling ABS modified materials, characterized in that: The invention is prepared by melt blending raw materials, wherein the raw materials contain, by weight, 100 parts of recycled ABS materials, 0.5 to 5 parts of unsaturated acid anhydride compounds, 5 to 30 parts of unsaturated rubbers and 0.2 to 2 parts of initiators.

2. The recycled ABS modified material according to claim 1, characterized in that: The unsaturated acid anhydride compound is selected from at least one of maleic anhydride, itaconic anhydride or acrylic anhydride; And / or, the unsaturated rubber is selected from at least one of styrene-butadiene rubber, nitrile-butadiene rubber or polybutadiene rubber; And / or, the initiator is an organic peroxide initiator or a high temperature resistant initiator; Preferably, the organic peroxide initiator is selected from at least one of dicumyl peroxide and benzoyl peroxide; Preferably, the high temperature resistant initiator is selected from at least one of 2,3-dimethyl-2,3-diphenyl-butane and 2,3-diethyl-2,3-diphenyl-pentane.

3. The recycled ABS modified material according to claim 1 or 2, characterized in that: The tensile strength of the recycled ABS modified material is ≥48MPa, and / or the flexural strength is ≥64MPa, and / or the impact strength is ≥12.0kJ / m 2 .

4. A preparation method for recycling ABS modified materials, characterized in that: The preparation method comprises the following steps: a) subjecting a mixture I containing recycled ABS material and unsaturated acid anhydride compounds to melt blending I and forming and curing I to obtain an intermediate modified with the unsaturated acid anhydride compounds; b) melt blending II, molding and curing II of a mixture II containing the intermediate, unsaturated rubber and initiator.

5. The preparation method according to claim 4, characterized in that: Calculated by weight, the ratio of the recycled ABS material to the unsaturated anhydride compound, the unsaturated rubber and the initiator is 100:0.5-5:5-30:0.2-2.

6. The preparation method according to claim 4 or 5, characterized in that: The unsaturated acid anhydride compound is selected from at least one of maleic anhydride, itaconic anhydride or acrylic anhydride; And / or, the unsaturated rubber is selected from at least one of styrene-butadiene rubber, nitrile-butadiene rubber or polybutadiene rubber; And / or, the initiator is selected from at least one of dicumyl peroxide, benzoyl peroxide, 2,3-dimethyl-2,3-diphenyl-butane or 2,3-diethyl-2,3-diphenyl-pentane.

7. The preparation method according to any one of claims 4 to 6, characterized in that: The temperature of the melt blending I is 200-220° C.; And / or, the temperature of the melt blending II is 180-200°C.

8. The preparation method according to any one of claims 4 to 7, characterized in that: In the step a), the recycled ABS material is crushed and sieved to obtain flakes, and the maximum size of the flakes does not exceed 10 mm.

9. A recycled ABS modified material obtained by the preparation method according to any one of claims 4 to 8.

10. The recycled ABS modified material according to claim 9, characterized in that: The tensile strength of the recycled ABS modified material is ≥48MPa, and / or the flexural strength is ≥64MPa, and / or the impact strength is ≥12.0kJ / m 2 .

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