Aging-resistant ABS plastic material and preparation method thereof

Abstract

The application relates to an anti-aging ABS plastic material and a preparation method thereof, and belongs to the technical field of ABS composite materials. The anti-aging ABS plastic material is composed of the following components: AS resin 10-15 wt%, filler 8-12 wt%, compatibility agent 1.4-1.9 wt%, repair type anti-aging agent 0.12-0.17 wt%, hindered phenol antioxidant 0.07-0.1 wt% and lubricant 0.9-1.2 wt%, and the balance is ABS resin; the repair type anti-aging agent is based on a tetramethylpiperidine amine matrix, and is modified by sequentially introducing long-chain alkyl alkenyl and dithiol end mercapto groups; the repair type anti-aging agent has high polarity matching degree with the ABS matrix, can be uniformly dispersed in the ABS matrix, and can significantly improve the anti-aging performance of the ABS material through a double bond repair and free radical synergistic inhibition mechanism.

Description

TECHNICAL FIELD

[0001] The application belongs to the technical field of ABS composite materials, and particularly relates to an anti-aging ABS plastic material and a preparation method thereof. BACKGROUND

[0002] ABS (acrylonitrile-butadiene-styrene copolymer) is widely used in the fields of automobiles, home appliances and electronic devices due to its excellent mechanical properties, processing properties and cost advantages. However, the residual butadiene double bond in the ABS molecular chain is prone to free radical chain reaction under light, high temperature or oxidation environment, which leads to yellowing, embrittlement and mechanical property decline of the material, and seriously affects the service life. To solve this problem, the traditional method usually adds a hindered amine light stabilizer (HALS) as an anti-aging agent to inhibit the oxidation reaction by capturing free radicals. However, the existing HALS has the following limitations: the traditional HALS has high polarity and poor compatibility with the ABS matrix, and is prone to agglomeration or migration and precipitation, resulting in uneven distribution of the anti-aging agent and significant performance degradation after long-term use; and the free radical capture mechanism cannot repair the existing double bond defects in the ABS molecular chain, and lacks targeted protection for the secondary oxidation caused by high-temperature shearing in the processing process. SUMMARY

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

[0004] The purpose of the present application can be achieved by the following technical solutions:

[0005] An anti-aging ABS plastic material, which comprises the following components: 10-15 wt% of AS resin, 8-12 wt% of filler, 1.4-1.9 wt% of compatibility agent, 0.12-0.17 wt% of repair type anti-aging agent, 0.07-0.1 wt% of hindered phenolic antioxidant and 0.9-1.2 wt% of lubricant, and the balance of ABS resin.

[0006] The repair type anti-aging agent is prepared by the following method:

[0007] Step A1: 10-bromo-1-decene, tetramethylpiperidylamine and anhydrous tetrahydrofuran are pre-mixed, dry nitrogen is introduced for protection, the temperature is controlled by water bath at 40-50 DEG C, triethylamine is slowly added and stirred for 3-4 h, and then the temperature is increased to reflux for 1-1.5 h, the reaction is stopped, tetrahydrofuran is removed by rotary evaporation, and an intermediate is obtained;

[0008] Further, the feeding ratio of tetramethylpiperidylamine, 10-bromo-1-decene, triethylamine and anhydrous tetrahydrofuran is 10 mmol: 20 mmol: 4-6 mL: 35-50 mL, the active amino group of 10-bromo-1-decene and tetramethylpiperidylamine is fully substituted, and an alkenyl structure containing an alkyl chain is introduced.

[0009] Step A2: Premix the intermediate, azobisisobutyronitrile and acetone, heat to 50-60°C, stir and activate for 15-20 minutes, cool to room temperature and apply 550-700 mW / cm 2 UV irradiation, adding ethanedithiol and stirring to react for 5-7 hours, after the reaction is completed, acetone is evaporated under reduced pressure to remove, the substrate is washed with ethanol and aqueous solution, the aqueous phase is separated and vacuum dried to obtain a repairing anti-aging agent;

[0010] Furthermore, the feed ratio of the intermediate, ethanedithiol, azobisisobutyronitrile and acetone is 10 mmol: 25-30 mmol: 10-15 mg: 80-110 mL. Azobisisobutyronitrile activates the olefinic group introduced into the intermediate molecule, and then undergoes click addition with an excess of ethanedithiol under ultraviolet light initiation to introduce terminal thiol structural modification.

[0011] Furthermore, the compatibilizer is styrene-maleic anhydride copolymer.

[0012] Furthermore, the hindered phenol antioxidant is antioxidant 1076.

[0013] Furthermore, the lubricant is a mixture of polyethylene wax and calcium stearate.

[0014] A method for preparing an aging-resistant ABS plastic material comprises the following steps: premixing ABS resin and AS resin, adding a compatibilizer, a repairing anti-aging agent, a hindered phenol antioxidant, and a lubricant, and uniformly mixing the mixture; adding a filler during plasticizing and extruding the mixture, and then mixing and granulating the mixture to obtain the aging-resistant ABS plastic material.

[0015] Furthermore, the temperature parameters during the plasticizing and extruding process are 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.

[0016] Beneficial effects of the present invention:

[0017] The present invention synthesizes a repairing anti-aging agent through molecular design. Based on a tetramethylpiperidinamine matrix, an alkenyl structure containing an alkyl chain is introduced by replacing 10-bromo-1-decene with the tetramethylpiperidinamine matrix, and then a terminal thiol group is introduced through dithiol end-capping to significantly improve the aging resistance of the ABS material. The specific improvement effect is as follows: by introducing a long-chain alkyl group into the repairing anti-aging agent, the polarity matching degree between the repairing anti-aging agent and the ABS matrix is ​​improved, the compatibility is greatly improved, agglomeration or migration and precipitation is avoided, and uniform dispersion in the ABS matrix is ​​ensured; thanks to the good dispersibility, during the blending process, the terminal thiol group of the repairing anti-aging agent is more likely to undergo an addition reaction with the residual double bond in the ABS molecular chain, directly repairing the double bond defects that are prone to aging, reducing free radical generation sites from the source, and 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-lasting free radical capture capability. BRIEF DESCRIPTION OF THE DRAWINGS

[0018] In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the following briefly introduces the drawings required for describing the embodiments. Obviously, the drawings described below are only some embodiments of the present invention. For ordinary technicians in this field, other drawings can be obtained based on these drawings without creative work.

[0019] Figure 1 The graphs are the changing curves of L value and b value during the aging process of Example 4 of the present invention and the comparative example. DETAILED DESCRIPTION

[0020] The following will clearly and completely describe the technical solutions in the embodiments of the present invention in conjunction with the accompanying drawings. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without making any creative efforts shall fall within the scope of protection of the present invention.

[0021] Example 1: Preparation of aging-resistant ABS plastic material, specifically as follows:

[0022] (1) Preparation of restorative anti-aging agents

[0023] Step A1: 10-bromo-1-decene, tetramethylpiperidinamine, and anhydrous tetrahydrofuran were premixed, and dry nitrogen was introduced for protection. The temperature of the water bath was controlled at 50°C, and stirring was performed at 120 rpm. Triethylamine was slowly added to react for 3 hours, and then the temperature was raised to 65°C for reflux reaction for 1 hour. The feed ratio of tetramethylpiperidinamine, 10-bromo-1-decene, triethylamine, and anhydrous tetrahydrofuran was 10 mmol:20 mmol:6 mL:50 mL. After the reaction, tetrahydrofuran was removed by rotary evaporation to obtain an intermediate.

[0024] 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 700 mW / cm 2 The reaction mixture was subjected to ultraviolet irradiation, the stirring rate was reduced to 90 rpm, and ethanedithiol was added to react for 5 h. The feed ratio of the intermediate, ethanedithiol, azobisisobutyronitrile and acetone was 10 mmol:30 mmol:15 mg:110 mL. After the reaction was completed, 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 vacuum dried to obtain a repairing anti-aging agent.

[0025] (2) Preparation of aging-resistant ABS plastic materials

[0026] Ingredients: The raw materials are calculated by weight percentage: 10 wt % AS resin, which is a Lustran SAN 29 resin raw material; 12 wt % filler, which is a LP-700 lipophilic calcium carbonate; 1.9 wt % compatibilizer, which is a SMA-1000 styrene-maleic anhydride copolymer; 0.12 wt % repair-type antioxidant, which is prepared in this embodiment; 0.1 wt % hindered phenol antioxidant, which is a commercially available antioxidant 1076; 1.2 wt % lubricant, which is a mixture of industrial-grade calcium stearate and PE100 polyethylene wax in a weight ratio of 3:1; the balance 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 2: Preparation of aging-resistant ABS plastic material, specifically as follows:

[0029] (1) Preparation of restorative anti-aging agents

[0030] Step A1: Premix 10-bromo-1-decene, tetramethylpiperidinamine, and anhydrous tetrahydrofuran, introduce dry nitrogen protection, control the temperature in a water bath at 40°C, stir at 90 rpm, slowly add triethylamine and react for 4 hours, then raise the temperature to 65°C and reflux for 1.5 hours. The feed ratio of tetramethylpiperidinamine, 10-bromo-1-decene, triethylamine, and anhydrous tetrahydrofuran is 10 mmol:20 mmol:4 mL:35 mL. After the reaction, remove tetrahydrofuran by rotary evaporation to obtain an intermediate.

[0031] 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 reaction mixture was subjected to ultraviolet irradiation, and the stirring rate was reduced to 90 rpm. Ethanedithiol was added and the reaction was carried out for 7 h. The feed ratio of the intermediate, ethanedithiol, azobisisobutyronitrile and acetone was 10 mmol: 25 mmol: 10 mg: 80 mL. After the reaction was completed, 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 anti-aging agent.

[0032] (2) Preparation of aging-resistant ABS plastic materials

[0033] Ingredients: The raw materials are calculated by weight percentage: 15wt% AS resin, which is a Lustran SAN 29 resin raw material; 8wt% filler, which is LP-700 lipophilic calcium carbonate; 1.4wt% compatibilizer, which is SMA-1000 styrene-maleic anhydride copolymer; 0.17wt% repair-type anti-aging agent, which is prepared in this embodiment; 0.07wt% hindered phenol antioxidant, which is commercially available antioxidant 1076; 0.9wt% lubricant, which is a mixture of industrial-grade calcium stearate and PE100 polyethylene wax in a weight ratio of 3:1; the balance is ABS resin, which is Toyolac™ 950 X02 U-type resin raw material.

[0034] 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.

[0035] Example 3: Preparation of aging-resistant ABS plastic material, specifically as follows:

[0036] (1) Preparation of restorative anti-aging agents

[0037] Step A1: Take 10-bromo-1-decene, tetramethylpiperidinamine and anhydrous tetrahydrofuran, and mix them. Protect them with dry nitrogen gas, control the temperature at 50°C with a water bath, and stir them at 120 rpm. Slowly add triethylamine to react for 3.5 hours. Then, increase the temperature to 65°C to reflux for 1.2 hours. The feeding ratio of tetramethylpiperidinamine, 10-bromo-1-decene, triethylamine and anhydrous tetrahydrofuran is 10 mmol: 20 mmol: 5 mL: 45 mL. After the reaction is completed, remove tetrahydrofuran by rotary evaporation to obtain an intermediate.

[0038] Step A2: Take the intermediate, azobisisobutyronitrile and acetone, and mix them. Increase the temperature to 60°C, and stir them at 180 rpm for 15 minutes. Cool them to room temperature, and apply 600 mW / cm2ultraviolet radiation. Reduce the stirring speed to 90 rpm, and add ethanedithiol to react for 6 hours. The feeding ratio of the intermediate, ethanedithiol, azobisisobutyronitrile and acetone is 10 mmol: 25 mmol: 12 mg: 100 mL. After the reaction is completed, remove acetone by evaporation under reduced pressure. Add 30 vol% of an ethanol aqueous solution to the substrate to mix and wash. Separate the aqueous phase and dry it under vacuum to obtain a repair type anti-aging agent. 2 Ultraviolet radiation, reduce the stirring speed to 90 rpm, and add ethanedithiol to react for 6 hours. The feeding ratio of the intermediate, ethanedithiol, azobisisobutyronitrile and acetone is 10 mmol: 25 mmol: 12 mg: 100 mL. After the reaction is completed, remove acetone by evaporation under reduced pressure. Add 30 vol% of an ethanol aqueous solution to the substrate to mix and wash. Separate the aqueous phase and dry it under vacuum to obtain a repair type anti-aging agent.

[0039] (2) Preparation of an anti-aging ABS plastic material

[0040] Ingredients: Take raw materials according to the weight percentage. The AS resin is 12 wt%, and Lustran SAN 29 type resin raw material is selected. The filler is 10 wt%, and LP-700 type lipophilic calcium carbonate is selected. The compatibilizer is 1.6 wt%, and SMA-1000 type styrene-maleic anhydride copolymer is selected. The repair type anti-aging agent is 0.15 wt%, and is self-made in this embodiment. The hindered phenol antioxidant is 0.09 wt%, and commercially available antioxidant 1076 is selected. The lubricant is 1.1 wt%, and industrial grade calcium stearate and PE100 type polyethylene wax are mixed according to a weight ratio of 3:1. The rest is ABS resin, and Toyolac™950 X02 U type resin raw material is selected.

[0041] Mixing: Mix the ABS resin and the AS resin, and then add the compatibilizer, the repair type anti-aging agent, the hindered phenol antioxidant and the lubricant. Mix them uniformly. Put the mixture into the main feeding port of the twin-screw extruder, and put the filler into the side feeding port. Control the feeding section at 170±5°C, the compression section at 210±5°C, the metering section at 220±10°C, and the die head at 200±10°C. Extrude and granulate by plasticizing to obtain an anti-aging ABS plastic material.

[0042] Example 4, preparation of an anti-aging ABS plastic material, as follows:

[0043] (1) Preparation of a repair type anti-aging agent

[0044] Step A1: Premix 10-bromo-1-decene, tetramethylpiperidinamine, and anhydrous tetrahydrofuran, introduce dry nitrogen protection, control the temperature of the water bath at 45°C, stir at 120 rpm, slowly add triethylamine and react for 3.5 hours, then raise the temperature to 65°C and reflux for 1.5 hours, wherein the feed ratio of tetramethylpiperidinamine, 10-bromo-1-decene, triethylamine, and anhydrous tetrahydrofuran is 10 mmol:20 mmol:6 mL:40 mL. After the reaction, remove tetrahydrofuran by rotary evaporation to obtain an intermediate.

[0045] 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 The reaction mixture was irradiated with ultraviolet light, and the stirring rate was reduced to 90 rpm. Ethanedithiol was added and the reaction was carried out for 5.5 h. 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. 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 anti-aging agent.

[0046] (2) Preparation of aging-resistant ABS plastic materials

[0047] Ingredients: The raw materials are calculated by weight percentage: 12 wt % AS resin, which is a Lustran SAN 29 resin raw material; 11 wt % filler, which is a LP-700 lipophilic calcium carbonate; 1.7 wt % compatibilizer, which is a SMA-1000 styrene-maleic anhydride copolymer; 0.16 wt % repair-type antioxidant, which is prepared in this embodiment; 0.08 wt % hindered phenol antioxidant, which is a commercially available antioxidant 1076; 1 wt % 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.

[0048] 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.

[0049] As a comparative example, referring to Example 4, the repair anti-aging agent was replaced by the light stabilizer UV-3853, and the rest of the implementation process was exactly the same.

[0050] The plastic material was sampled from the above, and a flat vulcanizing machine was used to hot press form a sample at 230℃ and 10MPa; the sample was accelerated aging: according to GB / T 14522-2008 standard, wavelength 280-400nm, irradiation power 300W, environmental temperature 53±3℃, test period 720h; the initial tensile strength σ0, initial elongation at break ε0, tensile strength σ1 and elongation at break ε1 of the sample after aging were detected according to GB / T 1040.2-2022, and the L, a, b values of the aged sample were detected according to ISO 11664-4:2019 standard, see Table 1: tensile property test results before and after aging, Figure 1 : L and b value change curves during aging process of Example 4 and Comparative Example;

[0051] Table 1: tensile property test results before and after aging

[0052]

[0053] From the test results in Table 1, the initial mechanical properties of the examples and comparative examples are similar, and after 720h of accelerated aging, the mechanical properties of the comparative examples decrease more seriously, especially the elongation at break deteriorates significantly; according to the Figure 1 From the curve, it can be seen that the L value of Example 4 decreases lower and the b value increases less after aging, showing good long-term aging resistance, and from the curve it can be seen that the L and b values of Example 4 change slowly within 432h, having good aging slowing effect.

[0054] In the description of the specification, the description of the reference terms "one embodiment", "example", "specific example" and the like means that the specific features, structures, materials or characteristics described in conjunction with the embodiment or example are contained in at least one embodiment or example of the present application. In the present specification, the illustrative description of the above terms does not necessarily refer to the same embodiment or example. Moreover, the specific features, structures, materials or characteristics described can be combined in any one or more embodiments or examples in a suitable manner.

[0055] The above is only an example and description of the concept of the present application, and those skilled in the art can make various modifications or supplements or use similar ways to replace the described specific embodiments, as long as they do not deviate from the concept of the invention or exceed the scope defined by the present claims, which shall fall within the protection scope of the present application.

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 into the mixture, control the temperature in a water bath at 40-50°C, slowly add triethylamine, and stir to react for 3-4 hours. Then, raise the temperature to reflux for 1-1.5 hours. Upon completion of the reaction, 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 minutes, cool to room temperature and apply 550-700 mW / cm 2 UV irradiation, adding ethanedithiol and stirring to react for 5-7 hours, after the reaction is completed, acetone is evaporated under reduced pressure to remove, the substrate is washed with ethanol and aqueous solution, the aqueous phase is separated and vacuum dried to obtain a repairing anti-aging agent.

2. The aging-resistant ABS plastic material according to claim 1, characterized in that: The feeding 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 10 mmol: 25-30 mmol: 10-15 mg: 80-110 mL.

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; fillers are added during the plasticizing and extrusion process of the mixture and mixed and granulated to obtain an aging-resistant ABS plastic material.

8. The method for preparing an aging-resistant ABS plastic material according to claim 7, characterized in that: The temperature parameters during the plasticizing and extrusion 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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