Anti-aging ABS plastic material and preparation method thereof

Abstract

The invention relates to an anti-aging ABS (Acrylonitrile Butadiene Styrene) plastic material and a preparation method thereof, and belongs to the technical field of ABS composite materials. The anti-aging ABS plastic material is prepared from the following components in percentage by weight: 10 to 15 percent of AS (acrylonitrile-styrene) resin, 8 to 12 percent of filler, 1.4 to 1.9 percent of compatilizer, 0.12 to 0.17 percent of repair type anti-aging agent, 0.07 to 0.1 percent of hindered phenol antioxidant, 0.9 to 1.2 percent of lubricant and the balance of ABS resin, the repairing type anti-aging agent is based on a tetramethyl piperidylamine matrix, long-chain alkyl alkenyl and dithiol terminal sulfydryl are sequentially introduced for modification, the polarity matching degree of the repairing type anti-aging agent and an ABS matrix is high, the repairing type anti-aging agent can be evenly dispersed in the ABS matrix, and the repairing type anti-aging agent remarkably improves the aging resistance of the ABS material through a double-bond repairing and free radical synergistic inhibition mechanism.

Description

Technical Field

[0001] The present invention belongs to the technical field of ABS composite materials, and specifically relates to an anti-aging ABS plastic material and a preparation method thereof. Background Art

[0002] ABS (acrylonitrile-butadiene-styrene copolymer) is widely used in the fields of automobiles, household appliances, electronic devices, etc. due to its excellent mechanical properties, processing properties and cost advantages. However, the residual butadiene double bonds in the ABS molecular chain are prone to free radical chain reactions under light, high temperature or oxidative environments, resulting in yellowing, embrittlement of the material and a decrease in mechanical properties, seriously affecting its service life. To solve this problem, traditional methods usually add hindered amine light stabilizers (HALS) as anti-aging agents to inhibit oxidation reactions by capturing free radicals. However, the existing HALS have the following limitations: traditional HALS molecules have a relatively high polarity and poor compatibility with the ABS matrix, and are prone to agglomeration or migration and precipitation, resulting in uneven distribution of the anti-aging agent and significant performance attenuation after long-term use; relying only on the free radical capture mechanism, it is unable to repair the existing double bond defects in the ABS molecular chain, and lacks targeted protection against secondary oxidation caused by high-temperature shearing during the processing process. Summary of the Invention

[0003] In order to solve the technical problems mentioned in the background art, the purpose of the present invention is to provide an anti-aging ABS plastic material and a preparation method thereof.

[0004] The purpose of the present invention can be achieved by the following technical solutions: An anti-aging ABS plastic material, the components of which are: 10-15 wt% of AS resin, 8-12 wt% of filler, 1.4-1.9 wt% of compatibilizer, 0.12-0.17 wt% of repair-type anti-aging agent, 0.07-0.1 wt% of hindered phenol antioxidant and 0.9-1.2 wt% of lubricant, and the balance is ABS resin.

[0005] The repair-type anti-aging agent is prepared by the following method: Step A1: Premix 10-bromo-1-decene, tetramethylpiperidineamine and anhydrous tetrahydrofuran, introduce dry nitrogen for protection, control the temperature in a water bath at 40-50 °C, slowly add triethylamine and stir for reaction for 3-4 h, then raise the temperature to reflux for 1-1.5 h, and spin-evaporate to remove tetrahydrofuran after the reaction ends to obtain an intermediate; Further, the feeding ratio of tetramethylpiperidineamine, 10-bromo-1-decene, triethylamine and anhydrous tetrahydrofuran is 10 mmol: 20 mmol: 4-6 mL: 35-50 mL, and the active amino group of 10-bromo-1-decene is fully substituted with tetramethylpiperidineamine to introduce an alkenyl structure containing an alkyl chain.

[0006] Step A2: Premix the intermediate, azobisisobutyronitrile, and acetone, heat up to 50 - 60 °C, stir and activate for 15 - 20 min, cool to room temperature, apply 550 - 700 mW / cm 2 UV irradiation, add ethylene dithiol and stir to react for 5 - 7 h. After the reaction, evaporate and remove acetone under reduced pressure. Wash the substrate with an ethanol - aqueous solution mixture, separate the aqueous phase, and dry it under vacuum to obtain the repaired anti - aging agent; Furthermore, the feeding ratio of the intermediate, ethylene dithiol, azobisisobutyronitrile, and acetone is 10 mmol: 25 - 30 mmol: 10 - 15 mg: 80 - 110 mL. Azobisisobutyronitrile activates the alkenyl group introduced into the intermediate molecule, and then undergoes a click addition reaction with excessive ethylene dithiol under UV light initiation to introduce a terminal thiol structure for modification.

[0007] Furthermore, the compatibilizer is selected as styrene - maleic anhydride copolymer.

[0008] Furthermore, the hindered phenol antioxidant is selected as antioxidant 1076.

[0009] Furthermore, the lubricant is selected as a mixture of polyethylene wax and calcium stearate.

[0010] A preparation method of an aging - resistant ABS plastic material is as follows: Premix the ABS resin and AS resin, then add the compatibilizer, repaired anti - aging agent, hindered phenol antioxidant, and lubricant and mix them evenly. During the plasticizing and extrusion process of the mixture, add the filler and mix and granulate to obtain the aging - resistant ABS plastic material.

[0011] Furthermore, the temperature parameters during the plasticizing and extrusion process are set as follows: feeding section 170 ± 5 °C, compression section 210 ± 5 °C, metering section 220 ± 10 °C, and die head 200 ± 10 °C.

[0012] Advantages of the present invention: The present invention synthesizes a repaired anti - aging agent through molecular design. Based on the tetramethylpiperidineamine matrix, 10 - bromo - 1 - decene is used to introduce an alkenyl structure containing an alkyl chain through substitution, and then it is capped with dithiol to introduce terminal mercapto modification, significantly improving the aging resistance of the ABS material. The specific improvement effects are as follows: By introducing long - chain alkyl groups in the repaired anti - aging agent, the polarity matching degree with the ABS matrix is improved, greatly improving the compatibility, avoiding agglomeration or migration and precipitation, and ensuring uniform dispersion in the ABS matrix. Due to good dispersibility, during the blending process, the terminal mercapto groups of the repaired anti - aging agent are more likely to undergo an addition reaction with the residual double bonds in the ABS molecular chain, directly repairing the double - bond defects that are prone to cause aging, reducing the free - radical generation sites from the source. At the same time, through the double - bond repair reaction, the anti - aging agent molecules are anchored to the ABS matrix in the form of covalent bonds, significantly improving the stability of the hindered amine structure, avoiding molecular migration after long - term use, and achieving long - term free - radical scavenging ability. Brief Description of the Drawings

[0013] In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the following will briefly introduce the drawings required for the description of the embodiments. Obviously, the drawings in the following description are only some embodiments of the present invention. For those of ordinary skill in the art, without creative efforts, other drawings can be obtained based on these drawings.

[0014] Figure 1 It is a change curve of L value and b value during the aging process of Example 4 and Comparative Example of the present invention. Detailed Embodiments

[0015] The following will clearly and completely describe the technical solutions in the embodiments of the present invention with reference to the drawings in the embodiments of the present invention. Obviously, the described embodiments are only some embodiments of the present invention, rather than all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative efforts belong to the scope of protection of the present invention.

[0016] Example 1, Preparation of aging-resistant ABS plastic material, specifically as follows: (1) Preparation of repair-type anti-aging agent Step A1: Premix 10-bromo-1-decene, tetramethylpiperidineamine and anhydrous tetrahydrofuran, introduce dry nitrogen for protection, control the temperature in a water bath at 50 °C, stir at 120 rpm, slowly add triethylamine for reaction for 3 h, and then raise the temperature to 65 °C for reflux reaction for 1 h. Among them, the feeding ratio of tetramethylpiperidineamine, 10-bromo-1-decene, triethylamine and anhydrous tetrahydrofuran is 10 mmol: 20 mmol: 6 mL: 50 mL. After the reaction, evaporate tetrahydrofuran by rotary evaporation to obtain an intermediate.

[0017] Step A2: Premix the intermediate, azobisisobutyronitrile and acetone, raise the temperature to 60 °C, quickly stir and activate at 180 rpm for 15 min, cool to room temperature, apply 700 mW / cm 2 UV irradiation, reduce the stirring rate to 90 rpm, add ethanedithiol for reaction for 5 h. Among them, the feeding ratio of the intermediate, ethanedithiol, azobisisobutyronitrile and acetone is 10 mmol: 30 mmol: 15 mg: 110 mL. After the reaction, evaporate acetone under reduced pressure, add 30 vol% aqueous ethanol solution to the substrate for washing, separate the aqueous phase and dry it in vacuum to obtain a repair-type anti-aging agent.

[0018] (2) Preparation of aging-resistant ABS plastic material Ingredients: The raw materials are taken according to weight percentage, 10wt% of AS resin, which is a Lustran SAN 29 resin raw material; 12wt% of filler, which is a LP-700 lipophilic calcium carbonate; 1.9wt% of compatibilizer, which is a SMA-1000 styrene-maleic anhydride copolymer; 0.12wt% of repair anti-aging agent, which is homemade in this embodiment; 0.1wt% of hindered phenol antioxidant, which is a commercially available antioxidant 1076; 1.2wt% of lubricant, which is a mixture of industrial grade calcium stearate and PE100 polyethylene wax in a weight ratio of 3:1; the remainder is ABS resin, which is a Toyolac™950 X02 U-type resin raw material.

[0019] Mixing: premix ABS resin and AS resin, then add compatibilizer, repair anti-aging agent, hindered phenol antioxidant and lubricant to mix evenly, feed the mixture from the main feeding port of the twin-screw extruder, and feed the filler from the side feeding port. Control the feeding section at 170±5℃, the compression section at 210±5℃, the metering section at 220±10℃, and the die at 200±10℃. Through plasticizing, extrusion and granulation, the aging-resistant ABS plastic material is obtained.

[0020] Example 2, preparation of aging-resistant ABS plastic material, as follows: (1) Preparation of restorative antioxidants Step A1: premix 10-bromo-1-decene, tetramethylpiperidinamine and anhydrous tetrahydrofuran, introduce dry nitrogen for protection, control the temperature of the water bath at 40°C, stir at 90rpm, slowly add triethylamine to react for 4h, then heat to 65°C for reflux reaction for 1.5h, wherein the feed ratio of tetramethylpiperidinamine, 10-bromo-1-decene, triethylamine and anhydrous tetrahydrofuran is 10mmol:20mmol:4mL:35mL, and after the reaction is completed, remove tetrahydrofuran by rotary evaporation to obtain an intermediate.

[0021] Step A2: Premix the intermediate, azobisisobutyronitrile and acetone, heat to 50°C, stir rapidly at 150 rpm for 20 min, cool to room temperature and apply 550 mW / cm 2 The mixture was irradiated with ultraviolet light, and the stirring rate was reduced to 90 rpm. Ethylene dithiol was added to react for 7 h, wherein the feed ratio of the intermediate, ethylene dithiol, azobisisobutyronitrile and acetone was 10 mmol: 25 mmol: 10 mg: 80 mL. After the reaction, the acetone was evaporated under reduced pressure to remove the acetone. A 30 vol% ethanol aqueous solution was added to the substrate for washing. The aqueous phase was separated and dried in vacuo to obtain a repairing antioxidant.

[0022] (2) Preparation of aging-resistant ABS plastic materials Ingredients: The raw materials are calculated according to weight percentage, 15wt% of AS resin, which is a Lustran SAN 29 resin raw material; 8wt% of filler, which is a LP-700 lipophilic calcium carbonate; 1.4wt% of compatibilizer, which is a SMA-1000 styrene-maleic anhydride copolymer; 0.17wt% of repair anti-aging agent, which is prepared in this embodiment; 0.07wt% of hindered phenol antioxidant, which is a commercially available antioxidant 1076; 0.9wt% of lubricant, which is a mixture of industrial-grade calcium stearate and PE100 polyethylene wax in a weight ratio of 3:1; the remainder is ABS resin, which is a Toyolac™950 X02 U-type resin raw material.

[0023] Mixing: premix ABS resin and AS resin, then add compatibilizer, repair anti-aging agent, hindered phenol antioxidant and lubricant to mix evenly, feed the mixture from the main feeding port of the twin-screw extruder, and feed the filler from the side feeding port. Control the feeding section at 170±5℃, the compression section at 210±5℃, the metering section at 220±10℃, and the die at 200±10℃. Through plasticizing, extrusion and granulation, the aging-resistant ABS plastic material is obtained.

[0024] Example 3, preparation of aging-resistant ABS plastic material, as follows: (1) Preparation of restorative antioxidants Step A1: premix 10-bromo-1-decene, tetramethylpiperidinamine and anhydrous tetrahydrofuran, introduce dry nitrogen for protection, control the temperature of the water bath to 50°C, stir at 120rpm, slowly add triethylamine to react for 3.5h, then heat to 65°C for reflux reaction for 1.2h, wherein the feed ratio of tetramethylpiperidinamine, 10-bromo-1-decene, triethylamine and anhydrous tetrahydrofuran is 10mmol:20mmol:5mL:45mL, and after the reaction is completed, remove tetrahydrofuran by rotary evaporation to obtain an intermediate.

[0025] Step A2: Premix the intermediate, azobisisobutyronitrile and acetone, heat to 60°C, stir rapidly at 180 rpm for 15 min, cool to room temperature and apply 600 mW / cm 2 UV irradiation was performed, and the stirring rate was reduced to 90 rpm. Ethylene dithiol was added to react for 6 h, wherein the feed ratio of the intermediate, ethylene dithiol, azobisisobutyronitrile and acetone was 10 mmol: 25 mmol: 12 mg: 100 mL. After the reaction was completed, the acetone was evaporated under reduced pressure to remove the acetone, and a 30 vol% ethanol aqueous solution was added to the substrate for washing. The aqueous phase was separated and dried in vacuo to obtain a repairing antioxidant.

[0026] (2) Preparation of aging-resistant ABS plastic materials Ingredients: The raw materials are taken according to weight percentage, 12wt% of AS resin, which is a Lustran SAN 29 resin raw material; 10wt% of filler, which is a LP-700 lipophilic calcium carbonate; 1.6wt% of compatibilizer, which is a SMA-1000 styrene-maleic anhydride copolymer; 0.15wt% of repair anti-aging agent, which is homemade in this embodiment; 0.09wt% of hindered phenol antioxidant, which is a commercially available antioxidant 1076; 1.1wt% of lubricant, which is a mixture of industrial grade calcium stearate and PE100 polyethylene wax in a weight ratio of 3:1; the remainder is ABS resin, which is a Toyolac™950 X02 U-type resin raw material.

[0027] Mixing: premix ABS resin and AS resin, then add compatibilizer, repair anti-aging agent, hindered phenol antioxidant and lubricant to mix evenly, feed the mixture from the main feeding port of the twin-screw extruder, and feed the filler from the side feeding port. Control the feeding section at 170±5℃, the compression section at 210±5℃, the metering section at 220±10℃, and the die at 200±10℃. Through plasticizing, extrusion and granulation, the aging-resistant ABS plastic material is obtained.

[0028] Example 4, preparation of aging-resistant ABS plastic material, as follows: (1) Preparation of restorative antioxidants Step A1: premix 10-bromo-1-decene, tetramethylpiperidinamine and anhydrous tetrahydrofuran, introduce dry nitrogen for protection, control the temperature of the water bath to 45°C, stir at 120rpm, slowly add triethylamine to react for 3.5h, then heat to 65°C for reflux reaction for 1.5h, wherein the feed ratio of tetramethylpiperidinamine, 10-bromo-1-decene, triethylamine and anhydrous tetrahydrofuran is 10mmol:20mmol:6mL:40mL, and after the reaction is completed, remove tetrahydrofuran by rotary evaporation to obtain an intermediate.

[0029] Step A2: Premix the intermediate, azobisisobutyronitrile and acetone, heat to 55°C, stir rapidly at 180 rpm for 15 min, cool to room temperature and apply 650 mW / cm 2 Under ultraviolet irradiation, the stirring rate was reduced to 90 rpm, and ethanedithiol was added to react for 5.5 hours, wherein the feed ratio of the intermediate, ethanedithiol, azobisisobutyronitrile and acetone was 10 mmol: 30 mmol: 10 mg: 100 mL. After the reaction was completed, the acetone was evaporated under reduced pressure to remove the acetone, and a 30 vol% ethanol aqueous solution was added to the substrate for washing, and the aqueous phase was separated and dried in vacuo to obtain a repairing antioxidant.

[0030] (2) Preparation of aging-resistant ABS plastic materials Ingredients: The raw materials are taken according to weight percentage, 12wt% of AS resin, which is a Lustran SAN 29 resin raw material; 11wt% of filler, which is a LP-700 lipophilic calcium carbonate; 1.7wt% of compatibilizer, which is a SMA-1000 styrene-maleic anhydride copolymer; 0.16wt% of repair anti-aging agent, which is prepared in this embodiment; 0.08wt% of hindered phenol antioxidant, which is a commercially available antioxidant 1076; 1wt% of lubricant, which is a mixture of industrial-grade calcium stearate and PE100 polyethylene wax in a weight ratio of 3:1; the remainder is ABS resin, which is a Toyolac™950 X02 U-type resin raw material.

[0031] Mixing: premix ABS resin and AS resin, then add compatibilizer, repair anti-aging agent, hindered phenol antioxidant and lubricant to mix evenly, feed the mixture from the main feeding port of the twin-screw extruder, and feed the filler from the side feeding port. Control the feeding section at 170±5℃, the compression section at 210±5℃, the metering section at 220±10℃, and the die at 200±10℃. Through plasticizing, extrusion and granulation, the aging-resistant ABS plastic material is obtained.

[0032] As a comparative example, referring to Example 4, the restorative anti-aging agent is replaced by the light stabilizer UV-3853, and the rest of the implementation process is exactly the same.

[0033] Samples were taken from the above plastic materials and hot-pressed at 230°C and 10MPa using a flat vulcanizer; accelerated aging of the samples: refer to GB / T 14522-2008 standard, wavelength 280-400nm, irradiation power 300W, ambient temperature 53±3°C, and test cycle 720h; refer to GB / T 1040.2-2022 to test the initial tensile strength σ0, initial elongation at break ε0, tensile strength σ1 after aging, and elongation at break ε1 after aging of the samples, refer to ISO 11664-4:2019 standard to test the L, a, and b values ​​of the aged samples, as shown in Table 1: Tensile performance test results before and after aging, Figure 1 : L value and b value change curves during aging of Example 4 and Comparative Example; Table 1: Tensile properties test results before and after aging

[0034] From the test results in Table 1, it can be seen that the initial mechanical properties of the embodiment and the comparative example are similar. After 720h accelerated aging, the mechanical properties of the comparative example deteriorate more seriously, especially the elongation at break deteriorates significantly. Figure 1It can be seen from the curve that in Example 4, the decrease in the L value after aging is lower and the increase in the b value is less, showing good long-term aging resistance. Moreover, it can be seen from the curve that within the 432h cycle, the changes in the L and b values of Example 4 are slow, having a good effect of slowing down aging.

[0035] In the description of the specification, the description with reference to terms such as "one embodiment", "example", "specific example", etc. means that the specific features, structures, materials or characteristics described in connection with the embodiment or example are included in at least one embodiment or example of the present invention. In this specification, the schematic expressions of the above terms do not necessarily refer to the same embodiment or example. Moreover, the specific features, structures, materials or characteristics described can be combined in a suitable manner in any one or more embodiments or examples.

[0036] The above content is only an example and illustration of the concept of the present invention. Those skilled in the art of this technology can make various modifications or supplements to the specific embodiments described or use similar ways to replace them. As long as they do not deviate from the concept of the invention or exceed the scope defined by this claim book, they should all belong to the protection scope of the present invention.

Claims

1. An aging-resistant ABS plastic material, characterized in that: The specific components are: AS resin 10-15wt%, filler 8-12wt%, compatibilizer 1.4-1.9wt%, repair anti-aging agent 0.12-0.17wt%, hindered phenol antioxidant 0.07-0.1wt% and lubricant 0.9-1.2wt%, and the balance is ABS resin; The repairing anti-aging agent is prepared by the following method: Step A1: premix 10-bromo-1-decene, tetramethylpiperidinamine and anhydrous tetrahydrofuran, introduce dry nitrogen for protection, control the water bath temperature at 40-50°C, slowly add triethylamine and stir to react for 3-4h, then heat and reflux for 1-1.5h, and after the reaction is completed, remove tetrahydrofuran by rotary evaporation to obtain an intermediate; Step A2: premix the intermediate, azobisisobutyronitrile and acetone, heat to 50-60°C, stir and activate for 15-20 min, cool to room temperature and apply 550-700 mW / cm 2 The mixture was irradiated with ultraviolet light, and ethanedithiol was added and stirred for reaction for 5-7 hours. After the reaction was completed, the acetone was evaporated under reduced pressure to remove the acetone. The substrate was washed with ethanol and aqueous solution, and the aqueous phase was separated and dried in vacuo to obtain a repairing antioxidant.

2. The aging-resistant ABS plastic material according to claim 1, characterized in that: The feed ratio of tetramethylpiperidinamine, 10-bromo-1-decene, triethylamine and anhydrous tetrahydrofuran is 10 mmol: 20 mmol: 4-6 mL: 35-50 mL.

3. The aging-resistant ABS plastic material according to claim 2, characterized in that: The feed ratio of the intermediate, ethanedithiol, azobisisobutyronitrile and acetone is 10mmol:25-30mmol:10-15mg:80-110mL.

4. The aging-resistant ABS plastic material according to claim 1, characterized in that: The compatibilizer is styrene-maleic anhydride copolymer.

5. The aging-resistant ABS plastic material according to claim 1, characterized in that: The hindered phenol antioxidant is antioxidant 1076.

6. The aging-resistant ABS plastic material according to claim 1, characterized in that: The lubricant is a mixture of polyethylene wax and calcium stearate.

7. A method for preparing the aging-resistant ABS plastic material according to any one of claims 1 to 6, characterized in that: Specifically, ABS resin and AS resin are premixed, and then a compatibilizer, a repairing anti-aging agent, a hindered phenol antioxidant and a lubricant are added and mixed evenly. During the plasticizing and extruding process of the mixture, fillers are added and mixed and granulated to obtain an anti-aging ABS plastic material.

8. The method for preparing an aging-resistant ABS plastic material according to claim 7, characterized in that: The temperature parameters in the plasticizing and extruding process were set as follows: 170±5°C in the feeding section, 210±5°C in the compression section, 220±10°C in the metering section, and 200±10°C in the die head.

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