Anti-aging ABS (Acrylonitrile Butadiene Styrene) composite material for reflecting cover and preparation method thereof

Abstract

The invention discloses an anti-aging ABS composite material for a reflector and a preparation method thereof, and belongs to the technical field of ABS composites.The preparation method comprises the steps that graphene modified copper doped titanium cerium oxide composite powder is prepared through a sol-gel method, then antioxidant PAO (at) SMA microcapsules are prepared through a solvent evaporation method, the graphene modified copper doped titanium cerium oxide composite powder and the antioxidant PAO (at) SMA microcapsules are mixed with ABS-g-MAH, auxiliaries and ABS resin, and the anti-aging ABS composite material for the reflector is obtained. And finally, carrying out twin-screw extrusion granulation to prepare the anti-aging ABS composite material for the reflecting cover. The graphene modified copper doped titanium cerium oxide composite powder, the antioxidant PAO (at) SMA microcapsule and the ABS-g-MAH are matched, so that the synergistic effect of ultraviolet aging resistance, long-acting oxidation resistance and interfacial compatibility is achieved, the core defect of a traditional ABS material is overcome, the comprehensive performance of a reflecting cover is guaranteed, the product has ultraviolet yellowing resistance, mechanical stability and optical precision, and the service life of the reflecting cover is prolonged. And the requirements of the optical trapper on accurate light trapping, long-term weather resistance and structural reliability are met.

Description

TECHNICAL FIELD

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

[0002] A reflector is a kind of optical functional component that converges light rays emitted by a light source into a directional light beam through specific geometric structures or surface treatments. Its core function is to improve light utilization and precisely control the illumination area, directly determining the light efficiency and use experience of devices in the fields of lighting, transportation, and optical capture. Currently, reflectors have been widely used in various scenarios, and as the demand for "high efficiency and energy saving" and "long-life devices" upgrades, higher requirements are placed on the weather resistance, mechanical stability, and optical precision of reflectors.

[0003] In the selection of the base material of the reflector, ABS resin, i.e., acrylonitrile-butadiene-styrene copolymer, has become one of the mainstream choices due to its multi-dimensional performance advantages. Compared with metal base materials such as aluminum alloy and stainless steel, ABS resin has a low density and significant lightweight advantage, can quickly prepare complex optical curved surfaces through injection molding, and does not require subsequent precision polishing. Compared with ordinary PP and PS plastics, ABS resin has excellent impact strength and rigidity, can withstand minor collisions during transportation and installation, and reduces the risk of damage. Therefore, ABS resin has gradually replaced some metal and low-end plastic base materials and become the core base material for the preparation of mid-to-high-end reflectors. However, the polybutadiene segment in the ABS molecular chain contains a large number of unsaturated double bonds, which are easily oxidized and degraded under the action of ultraviolet light, high temperature, and oxygen, leading to yellowing, embrittlement, and significant decrease in mechanical properties of the material.

[0004] To address the problem of aging resistance, a Chinese invention patent with publication number CN104927286A discloses an anti-aging ABS composite material and a preparation method thereof. The scheme claims that by compounding specific anti-aging additives and modified components, the aging resistance stability of the material is significantly improved, and the composite material has excellent anti-aging performance. However, the heat-oxidation inhibitor N-cyclohexyl-p-methoxyaniline used in this scheme belongs to amine antioxidants. Although this type of additive can inhibit the thermal-oxidative degradation of ABS to some extent, it is prone to oxidative discoloration during processing at high temperatures and long-term use, thereby becoming a new source of yellowing and leading to the deterioration of optical performance of the reflector in a short period.

[0005] To meet the composite requirements of high reflectivity and low volatility of the reflector, a Chinese invention patent with publication number CN114891333B discloses a PC / ABS composite material, a preparation method and application thereof. This patent uses PC / ABS as the base material and introduces rutile titanium dioxide with high refractive index to improve the reflectivity, forming a composite system that meets the requirements of the reflector. Subsequently, the PC / ABS composite material is processed through injection molding, polishing, and other processes to obtain a reflector product.

[0006] However, the rutile titanium dioxide has strong light shielding property, in addition to the reflection effect, it will also absorb or reflect a large amount of ultraviolet light, resulting in that the added benzotriazole ultraviolet absorber in the system cannot contact enough ultraviolet light, and it is difficult to play the anti-aging role, and more importantly, the rutile titanium dioxide will generate strong oxidative free radicals after absorbing ultraviolet light, and these free radicals will further attack the ABS molecular chain, resulting in material oxidative degradation, and in the optical trap scene, such degradation will cause the brittleness and yellowing of the reflector, reduce the light signal convergence accuracy, and directly affect the accurate capture effect of the optical trap on the light signal. SUMMARY

[0007] The purpose of the present application is to provide an anti-aging ABS composite material for reflector and a preparation method thereof, which realizes the synergistic effect of anti-ultraviolet aging, long-term antioxidant and interface compatibility by the cooperation of graphene modified copper doped titanium cerium oxide composite powder, antioxidant PAO@SMA microcapsule and ABS-g-MAH, solves the core defects of traditional ABS composite material, guarantees the comprehensive performance required by the reflector, and makes the product have excellent anti-ultraviolet yellowing, mechanical stability and optical accuracy, which meets the needs of optical trap for accurate light signal capture, long-term weather resistance and structural reliability.

[0008] The purpose of the present application can be realized by the following technical scheme: A preparation method of an anti-aging ABS composite material for reflector, comprising the following steps: Step one: using SMA as wall material, antioxidant PAO as core material, gelatin and sodium dodecyl sulfate emulsified solution as water phase, and adopting solvent evaporation method, antioxidant PAO@SMA microcapsule is prepared.

[0009] Step two: graphene modified copper doped titanium cerium oxide composite powder, antioxidant PAO@SMA microcapsule, ABS-g-MAH, antioxidant, lubricant and ABS resin are blended, and then double screw extrusion granulation is carried out to obtain the anti-aging ABS composite material for reflector.

[0010] Further, the temperature of double screw extrusion is 180-230 DEG C.

[0011] Further, the antioxidant is any one of phosphite 168 and phosphite 164.

[0012] Further, the mass ratio of graphene modified copper doped titanium cerium oxide composite powder, antioxidant PAO@SMA microcapsule, ABS-g-MAH, antioxidant, lubricant and ABS resin is 3-7:1-3:1-2:0.2-0.4:0.3-0.5:90-110.

[0013] Further, the specific preparation steps of the graphene modified copper doped titanium cerium oxide composite powder are as follows: Under the stirring condition of 600-800 r / min, anhydrous ethanol and citric acid monohydrate are added into a stirring kettle, then tetrabutyl titanate and cerium nitrate hexahydrate are added and stirred for 30-60 min, then copper sulfate solution and graphene oxide are ultrasonically dispersed for 40-60 min and added dropwise into the stirring kettle, and after dropping, stirring is continued for 1-2 h to form a homogeneous sol, after standing for 24-48 h, vacuum freeze-drying is performed for 24-48 h, then the product is transferred into a muffle furnace, heated to 600-700 ℃ at a rate of 2 ℃ / min, and after heat preservation for 1-2 h, the furnace is cooled, and then grinding and sieving are performed to obtain the graphene modified copper doped titanium cerium oxide composite powder.

[0014] Further, the usage ratio of anhydrous ethanol, citric acid monohydrate, tetrabutyl titanate, cerium nitrate hexahydrate, copper sulfate solution and graphene oxide is 60-80 mL: 24-33 g: 15-25 mL: 23-30 g: 17-29 mL: 0.5-2 g.

[0015] Further, the copper sulfate solution is prepared from deionized water, ice ethanol, anhydrous ethanol and copper sulfate.

[0016] Further, the usage ratio of deionized water, ice ethanol, anhydrous ethanol and copper sulfate is 3-5 mL: 3-5 mL: 11-19 mL: 0.25-0.45 g.

[0017] Further, the specific preparation steps of the antioxidant PAO@SMA microcapsule are as follows: SMA, antioxidant PAO and dichloromethane are added into a reaction kettle, and at the same time, gelatin, sodium dodecyl sulfate and deionized water are mixed to form an aqueous phase which is added into the reaction kettle, and then the reaction is carried out at 500-700 r / min and 35-40 ℃ for 2.5-3.5 h, the product is filtered, the precipitate is washed with distilled water and anhydrous ethanol alternately for 2-3 times, and then drying is performed at 60-70 ℃ for 2.5-3.5 h to obtain the antioxidant PAO@SMA microcapsule.

[0018] Further, the usage ratio of SMA, antioxidant PAO, dichloromethane, gelatin, sodium dodecyl sulfate and deionized water is 2-4 g: 3-9 g: 60-100 mL: 3.2-4.8 g: 0.3-0.5 g: 160-240 mL.

[0019] The beneficial effects of the present application are as follows:

[0020] 1. The present application solves the core defects of traditional ABS retroreflective cover materials, such as yellowing and brittleness caused by the easy oxidative degradation of polybutadiene segment, discoloration caused by the easy oxidation of amine antioxidant, and the acceleration of ABS degradation caused by the generation of free radicals from rutile titanium dioxide, by constructing a ternary composite system of graphene modified copper doped titanium cerium oxide composite powder, antioxidant PAO@SMA microcapsule and ABS-g-MAH as a compatibilizer, and matching sol-gel method, solvent evaporation method and twin screw extrusion process.

[0021] 2. In the present application, the graphene modified copper doped titanium cerium oxide composite powder has a dual key role: first, copper cerium oxide efficiently absorbs ultraviolet light, and graphene can physically block the penetration of oxygen, thereby inhibiting the oxidative degradation of ABS molecular chains from the source and reducing the risk of yellowing and brittleness of the material; second, the composite powder has excellent dispersibility and can precisely control the particle size by sol-gel method, which can not only improve the visible light reflectivity of the composite material, but also reduce the haze, ensuring the optical precision of the retroreflective cover and effectively avoiding the defect of easy agglomeration of traditional rutile titanium dioxide which leads to high haze.

[0022] 3. In the present application, the added antioxidant PAO@SMA microcapsule can release antioxidant for a long time, the wall material can encapsulate the antioxidant PAO and prevent its migration and loss during short processing, and the SMA wall material can slowly release antioxidant to inhibit the thermal-oxidative aging of the ABS matrix in long-term aging scenarios; at the same time, the SMA contains a styrene segment which has good compatibility with the ABS matrix, and the uniform coating is ensured by the combination of gelatin and SDS emulsifier, avoiding the local antioxidant failure caused by uneven dispersion of antioxidant and maintaining the mechanical stability of the composite material.

[0023] 4. In the twin screw extrusion process of the present application, the maleic anhydride groups of ABS-g-MAH may react with the butadiene segment of the ABS matrix, the hydroxyl groups on the surface of the graphene modified copper doped titanium cerium oxide composite powder and the SMA in the shell of the antioxidant PAO@SMA microcapsule; at the same time, ABS-g-MAH and ABS matrix can enhance the affinity through segment entanglement; the dual effects of esterification reaction and segment entanglement not only promote the uniform dispersion of composite fillers and microcapsules in the matrix, but also strengthen the interfacial bonding force, ultimately realizing the deep synergy of ultraviolet absorption, oxygen barrier and long-term antioxidant function, so that the composite material has excellent anti-ultraviolet yellowing, mechanical stability and optical precision, which meets the use requirements of retroreflective cover. DETAILED DESCRIPTION

[0024] The technical solutions in the embodiments of the present application will be clearly and completely described below with reference to the embodiments of the present application. Obviously, the described embodiments are only a part of the embodiments of the present application, rather than all the embodiments of the present application. Based on the embodiments of the present application, all other embodiments obtained by those skilled in the art without creative work belong to the protection scope of the present application.

[0025] Embodiment 1: A preparation method of an anti-aging ABS composite material for a light reflector S1: 4 mL of deionized water, 4 mL of ice ethanol, 15 mL of anhydrous ethanol and 0.35 g of copper sulfate were mixed and dissolved to obtain a copper sulfate solution; 70 mL of anhydrous ethanol and 28.5 g of citric acid monohydrate were added to a stirring kettle and stirred and dissolved, then 20 mL of tetrabutyl titanate and 26.5 g of cerium nitrate hexahydrate were added and stirred for 45 min, then 23 mL of the copper sulfate solution and 1.25 g of graphene oxide were mixed, ultrasonically dispersed for 50 min at 300 W, and then added dropwise to the reaction kettle, and stirring was continued for 1.5 h after dropping to form a homogeneous sol, and then the sol was left to stand for 36 h, vacuum freeze-dried for 36 h, transferred to a muffle furnace, heated to 650 ℃ at a rate of 2 ℃ / min, kept for 1.5 h, and then cooled with the furnace, and the product after cooling was ground, sieved, and graphene-modified copper-doped titanium-cerium oxide composite powder was prepared.

[0026] The above step uses a sol-gel method to prepare the product. In this process, citric acid is used as a chelating agent, and tetrabutyl titanate and cerium nitrate hexahydrate are first coordinated in anhydrous ethanol to form a stable metal complex, and copper sulfate and graphene oxide are dispersed by mixing solvents; when the mixed solution of copper sulfate and graphene oxide is added dropwise into the solution containing the titanium-cerium complex after ultrasonic treatment, water initiates the hydrolysis of the titanium source, copper ions are simultaneously doped into the titanium-oxygen structure, and graphene oxide is uniformly dispersed; after stirring, a homogeneous sol is formed, and the gelation and drying are completed after standing; finally, the metal complex is decomposed into titanium dioxide and cerium oxide by high-temperature calcination, the copper doping controls the crystal form and band gap of titanium dioxide, and graphene oxide is simultaneously thermally reduced to reduced graphene oxide; after grinding and sieving, the graphene-modified copper-doped titanium-cerium oxide composite powder with a structure of 50-80 nm is finally formed.

[0027] S2: 3 g of styrene-maleic anhydride copolymer (SMA), 6 g of antioxidant PAO and 80 mL of dichloromethane were added to a reaction kettle to form an oil phase, and 4 g of gelatin, 0.4 g of sodium dodecyl sulfate and 200 mL of deionized water were mixed as an aqueous phase and added to the reaction kettle; the reaction was carried out at a speed of 600 r / min and a temperature of 35 ℃ for 3 h; after the organic solvent was volatilized, the product was filtered, the precipitate was washed with distilled water and anhydrous ethanol alternately for 3 times, and dried at 65 ℃ for 3 h to obtain antioxidant PAO@SMA microcapsules.

[0028] The above step is based on solvent evaporation method to prepare anti-aging PAO@SMA microcapsules. The styrene-maleic anhydride copolymer (SMA) is used as the wall material and the anti-aging PAO is used as the core material. The oil phase is formed by dissolving the anti-aging PAO in dichloromethane. The water phase is formed by dissolving the gelatin and sodium dodecyl sulfate (SDS) in deionized water. The oil phase is emulsified in the water phase to form an oil-in-water emulsion. The dichloromethane gradually evaporates, causing the SMA to precipitate on the surface of the anti-aging PAO to form a wall film. After washing and drying, the SMA-coated anti-aging PAO microcapsules are obtained. The gelatin and SDS work together to stabilize the emulsion and ensure uniform coating.

[0029] S3: After drying, 5g of graphene-modified copper-doped titanium cerium oxide composite powder, 2g of anti-aging PAO@SMA microcapsules, 1.5g of maleic anhydride grafted acrylonitrile-butadiene-styrene copolymer (ABS-g-MAH), 0.3g of antioxidant phosphite 168, and 0.4g of lubricant zinc stearate are sequentially added to a high-speed mixer. The temperature is 42℃ and the rotation speed is 650r / min. The mixture is blended for 2-3min. Then, 100g of dried ABS resin is added to the high-speed mixer and mixed for another 4.5min at a rotation speed of 800r / min. The anti-aging ABS composite material for the reflector is obtained.

[0030] S4: The anti-aging ABS composite material is added to a twin-screw extruder. The screw temperature is 180-230℃, the screw rotation speed is 500r / min, the vacuum negative pressure is -0.075MPa, and the melt pressure is 9Mpa. The material is melt-extruded and granulated to obtain the anti-aging ABS composite material for the reflector.

[0031] During the high-temperature melting process of the twin-screw extrusion, the maleic anhydride groups in the ABS-g-MAH and the anti-aging PAO@SMA microcapsule shell layer undergo ring-opening and esterification reaction with the active methylene hydrogen of the butadiene segment of the ABS resin, forming stable ester bonds. The hydroxyl and carboxyl groups on the surface of the graphene-modified copper-doped titanium cerium oxide composite powder can undergo esterification reaction with maleic anhydride, forming ester bonds. The molecular chain structure of ABS-g-MAH is highly similar to that of the ABS matrix, achieving affinity with the matrix through segment entanglement and van der Waals force. The structure of the anti-aging PAO@SMA microcapsule contains styrene segments, which have good compatibility with the ABS resin.

[0032] Examples 2-4: A method for preparing an anti-aging ABS composite material for a reflector, which is different from Example 1 in that the addition amount of the substances in step S1 is different, and the remaining steps and parameters remain the same. The specific addition amounts are shown in Table 1.

[0033] Table 1: Substance amount control table in step S1 Group Anhydrous ethanol (mL) Citric acid monohydrate (g) Tetrabutyl titanate (mL) Cerium nitrate hexahydrate (g) Copper sulfate solution (mL) Graphene oxide (g) Example 2 60 24 15 23 17 0.5 Example 3 72 29 22 27 23 1.3 Example 4 80 33 25 30 29 2.0 Example 5-Example 7: A method for preparing an anti-aging ABS composite material for a reflector, which is different from example 1 in that the amount of substances added in step S2 is different, and the remaining steps and parameters remain unchanged. The specific amount of addition is shown in Table 2.

[0034] Table 2: Substance usage control table in step S2 Group Styrene-maleic anhydride copolymer (g) Antioxidant PAO (g) Dichloromethane (mL) Gelatin (g) Sodium dodecyl sulfate (g) Deionized water (mL) Example 5 2 3 60 3.2 0.3 160 Example 6 3.5 7 90 4.2 0.4 210 Example 7 4 9 100 4.8 0.5 240 Example 8: A method for preparing an anti-aging ABS composite material for a reflector, which is different from example 1 in that the antioxidant phosphite 168 in step S3 is replaced by antioxidant phosphite 164, and the remaining steps and parameters remain unchanged.

[0035] The raw materials used in examples 1-8 of the present application are all commercially available. Among them, anhydrous ethanol, copper sulfate, zinc stearate and sodium dodecyl sulfate are purchased from Shanghai Maikelin Biotechnology Co., Ltd.; graphene oxide has a lateral size of 1-5 μm and a thickness of 0.5-1 nm, and is purchased from Beijing Fosman Technology Co., Ltd.; citric acid monohydrate, tetrabutyl titanate, gelatin and dichloromethane are purchased from Shanghai Aladdin Biochemical Co., Ltd.; cerium nitrate hexahydrate is purchased from National Pharmaceutical Group Chemical Reagent Co., Ltd.; styrene-maleic anhydride copolymer is purchased from Hubei Maiduohe Biotechnology Co., Ltd., the content of maleic anhydride is 15%, and the molecular weight is 15000-20000; antioxidant PAO is an antioxidant premixed oil supplied by Shanghai Nanokex New Energy Technology Co., Ltd., which is prepared by homogenization premixing process; ABS-g-MAH (maleic anhydride grafted ABS) is purchased from Heyuan Jinheng Chemical Co., Ltd.; phosphite 168 and phosphite 164 are purchased from Nanjing Kexulei Chemical Co., Ltd. ® PAO100 is prepared by homogenization premixing process; ABS-g-MAH (maleic anhydride grafted ABS) is purchased from Heyuan Jinheng Chemical Co., Ltd.; phosphite 168 and phosphite 164 are purchased from Nanjing Kexulei Chemical Co., Ltd.

[0036] Comparative Example 1: On the basis of example 1, step S1 is omitted, and the graphene modified copper doped cerium titanium oxide composite powder in step S3 is replaced by an equal amount of rutile titanium dioxide, and the other steps and parameters remain unchanged to obtain an ABS composite material.

[0037] Comparative Example 2: On the basis of example 1, step S2 is omitted, and only the antioxidant PAO@SMA microcapsule is removed in step S3, and the other materials and parameters remain unchanged to obtain an ABS composite material.

[0038] Comparative Example 3: On the basis of example 1, ABS-g-MAH is removed in step S3, and the other steps and parameters remain unchanged to obtain an ABS composite material.

[0039] The samples of the ABS composites prepared in Example 1-Example 8 and Comparative Example 1-Comparative Example 3 were tested for performance after injection molding, wherein the Charpy impact strength was determined according to the method specified in GB / T1043.1-2008 standard, the sample length was 80 mm, the width was 10 mm, the thickness was 4 mm, the notch type was A type, and the impact test machine was used to determine the material's ability to resist impact embrittlement; the tensile strength and elongation at break were determined according to the method specified in GB / T1040.2-2006 standard, the sample length was 165 mm, the test was completed at room temperature and a tensile speed of 50 mm / min, and the material's resistance to deformation was evaluated; the visible light reflectance was determined according to the method specified in GB / T2680-2021 standard, reflecting the material's ability to reflect visible light; the haze was determined according to the method specified in GB / T2410-2021 standard, evaluating the scattering degree of reflected light to ensure lighting accuracy; the weather resistance and yellowing resistance were tested by first aging the sample according to GB / T16422.2-2014 standard, and then testing the yellowing index ΔYI after aging according to GB / T2409-2021, to quantify the material's ability to resist ultraviolet yellowing. The test results are shown in Table 3: Table 3 Performance test results of ABS composite samples Group Charpy impact strength (kJ / m 2 )]> Tensile strength (MPa) Elongation at break (%) Visible light reflectance (%) Haze (%) Yellowing index (ΔYI) after xenon lamp aging Example 1 25.8 43.2 18.5 91.2 2.3 2.2 Example 2 24.5 41.8 17.8 89.5 2.7 2.5 Example 3 26.3 44.5 19.2 92.1 2.1 2.1 Example 4 25.1 42.6 18.1 90.3 2.5 2.3 Example 5 24.9 42.1 17.9 89.8 2.6 2.4 Example 6 26.0 43.8 18.7 91.5 2.2 2.2 Example 7 25.5 43.0 18.3 90.7 2.4 2.3 Example 8 26.1 44.2 18.9 91.8 2.2 2.0 Comparative Example 1 18.2 36.5 12.3 85.6 6.8 5.0 Comparative Example 2 20.3 39.1 14.5 88.2 3.5 5.5 Comparative Example 3 21.5 40.3 15.2 89.0 3.2 7.2 As can be seen from Table 3, Examples 1-8 use a composite anti-aging system of graphene-modified copper-doped titanium cerium oxide composite powder, antioxidant PAO@SMA microcapsules and ABS-g-MAH, and combine sol-gel method to control the particle size of the composite filler, solvent evaporation method to ensure uniformity of microcapsule coating, and double screw extrusion to realize esterification reaction of maleic anhydride groups and chain entanglement, finally achieving synergistic improvement of anti-aging ABS composite in ultraviolet yellowing resistance, mechanical stability and optical accuracy.

[0040] Examples 2-4 gradually optimize the barrier property of graphene, the ultraviolet absorption ability and dispersibility of copper cerium oxide in the composite filler by adjusting the amount of materials in step S1, proving that optimization of the component ratio of the composite filler can strengthen the synergistic effect of ultraviolet absorption, oxygen barrier and mechanical enhancement; Examples 5-7 gradually adapt the coating rate of antioxidant PAO@SMA microcapsules and the compatibility of ABS matrix by adjusting the amount of materials in step S2, and the data in the table confirm that a reasonable range of wall material-core material ratio can ensure long-term antioxidant and optical uniformity of microcapsules; Example 8 replaces the antioxidant phosphite 168 in step S3 with phosphite 164, because phosphite 164 has better thermal stability, its yellowing index after xenon lamp aging is the lowest among the examples, and the mechanical and optical properties are basically the same as those of Example 1, indicating that the replacement of functionally equivalent antioxidants can improve the adaptability of the material to high temperature processing.

[0041] The Charpy impact strength, tensile strength, and elongation at break of the sample in Comparative Example 1 are the lowest among all groups, which may be because the graphene-modified copper-doped titanium cerium oxide composite powder preparation process is omitted in step S1, and the rutile titanium dioxide is used to replace the composite filler. On the one hand, the oxygen barrier effect of graphene and the ultraviolet absorption capacity of copper cerium oxide are missing, and the light-shielding property of rutile titanium dioxide cannot resist ultraviolet aging, resulting in a significantly higher yellowing index after xenon lamp aging than in the examples, and the oxidizing free radicals generated by the absorption of ultraviolet light by titanium dioxide accelerate the degradation of ABS, resulting in a decrease in visible light reflectance. On the other hand, rutile titanium dioxide is prone to agglomeration, which destroys the interfacial bonding with the ABS matrix, resulting in the ABS composite material not meeting the optical precision requirements of the reflector and having a structural failure risk of breakage during transportation and installation.

[0042] The Charpy impact strength, tensile strength, and elongation at break of the sample in Comparative Example 2 are lower than in the examples, which may be because the antioxidant PAO@SMA microcapsule preparation process is omitted in step S2, and only the antioxidant system of phosphite 168 is retained. On the one hand, the long-term controlled-release antioxidant effect of the antioxidant PAO@SMA microcapsule is missing, and phosphite 168 as a small molecule antioxidant lacks the protection of the microcapsule wall material, which is prone to migration and loss in the ultraviolet and temperature change environment of the xenon lamp aging test, and cannot continuously capture the free radicals generated by the oxidation of the ABS molecular chain, resulting in premature failure of the antioxidant system. On the other hand, without SMA, the styrene segment of the antioxidant PAO@SMA microcapsule forms a segment entanglement with the ABS matrix, which weakens the interfacial bonding force and results in a comprehensive decline in mechanical properties. This result confirms the necessity of the PAO@SMA microcapsule for long-term antioxidant and mechanical enhancement synergy.

[0043] The Charpy impact strength and tensile strength of the sample in Comparative Example 3 are lower than in the examples, and the yellowing index significantly increases after xenon lamp aging, which may be because ABS-g-MAH is removed in step S3, and the esterification reaction of the maleic anhydride group with the butadiene segment of the ABS matrix and the hydroxyl group on the surface of the composite filler is missing. On the one hand, the graphene-modified copper-doped titanium cerium oxide composite powder and the PAO@SMA microcapsule are unevenly dispersed in the matrix, forming local stress concentration, which is prone to fracture from defects under stress, resulting in a decline in mechanical properties. On the other hand, the interfacial bonding defects make it easier for oxygen to penetrate during the aging process, accelerating the oxidative degradation of the ABS molecular chain, resulting in a significantly higher yellowing index after xenon lamp aging, and the visible light reflectance is only slightly higher than that of Comparative Example 1-Comparative Example 2. This result demonstrates the key role of ABS-g-MAH in improving filler dispersity, strengthening interfacial bonding, and ensuring the comprehensive performance of material mechanics and anti-aging.

[0044] It is to be understood that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting. It is also possible in the present disclosure that steps can be executed in different sequence where is graphically or explicitly stated or indicated. Further, it is also possible in some instances, to combine or omit certain steps. Additionally, certain materials can be replaced by other

[0045] While the embodiments of the application have been shown and described herein, it is to be understood that the application is not limited to these embodiments. Rather, it is to be understood that various modifications, changes, substitutions and alterations can be made to the embodiments without departing from the spirit and scope of the application.

Claims

1. A method for preparing an anti-aging ABS composite material for a reflector cover, characterized by, Prepared by the following steps: Step one: using SMA as wall material, antioxidant PAO as core material, gelatin and sodium dodecyl sulfate emulsified solution as water phase, antioxidant PAO@SMA microcapsules were prepared by solvent evaporation method; Step two: graphene modified copper doped titanium cerium oxide composite powder, antioxidant PAO@SMA microcapsules, ABS-g-MAH, antioxidant, lubricant and ABS resin were blended, and anti-aging ABS composite material for reflector was obtained by double screw extrusion granulation.

2. The method for preparing anti-aging ABS composite material for reflector according to claim 1, characterized in that, The temperature of the double screw extrusion is 180-230 DEG C.

3. The method for preparing an anti-aging ABS composite material for reflectors according to claim 1, characterized in that, The antioxidant is any one of phosphite 168 and phosphite 164.

4. The method for preparing an anti-aging ABS composite material for a reflector according to claim 1, characterized in that, The mass ratio of the graphene modified copper doped titanium cerium oxide composite powder, antioxidant PAO@SMA microcapsules, ABS-g-MAH, antioxidant, lubricant and ABS resin is 3-7 g:1-3 g:1-2 g:0.2-0.4 g:0.3-0.5 g:90-110 g.

5. The method for preparing an anti-aging ABS composite material for a reflector according to claim 1, characterized in that, The specific preparation steps of the graphene modified copper doped titanium cerium oxide composite powder are as follows: Under the stirring condition of 600-800 r / min, anhydrous ethanol and citric acid monohydrate were added into a stirring kettle, then tetrabutyl titanate and cerium nitrate hexahydrate were added and stirred for 30-60 min, then copper sulfate solution and graphene oxide were ultrasonically dispersed for 40-60 min and added dropwise into the stirring kettle, after dropping, the stirring was continued for 1-2 h to form a homogeneous sol, the sol was left to stand for 24-48 h, vacuum freeze-dried for 24-48 h, transferred into a muffle furnace, heated to 600-700 DEG C at a rate of 2 DEG C / min, kept for 1-2 h, then cooled with the furnace, ground, sieved, and the graphene modified copper doped titanium cerium oxide composite powder was obtained.

6. The method for preparing an anti-aging ABS composite material for a reflector according to claim 5, characterized in that, The usage ratio of the anhydrous ethanol, citric acid monohydrate, tetrabutyl titanate, cerium nitrate hexahydrate, copper sulfate solution and graphene oxide is 60-80 mL:24-33 g:15-25 mL:23-30 g:17-29 mL:0.5-2 g.

7. The method of claim 5, wherein the anti-aging ABS composite material for a reflector is prepared by adding 0.1 to 0.5 parts by weight of the anti-aging agent to 100 parts by weight of ABS resin, and then mixing the anti-aging agent with the ABS resin. The copper sulfate solution is prepared from deionized water, ice ethanol, anhydrous ethanol and copper sulfate; The usage ratio of the deionized water, ice ethanol, anhydrous ethanol and copper sulfate is 3-5 mL:3-5 mL:11-19 mL:0.25-0.45 g.

8. The method for preparing an anti-aging ABS composite material for a reflector according to claim 1, characterized in that, The specific preparation steps of the antioxidant PAO@SMA microcapsules are as follows: SMA, antioxidant PAO and dichloromethane were added into a reaction kettle, gelatin, sodium dodecyl sulfate and deionized water were mixed as water phase and added into the reaction kettle, the reaction was carried out at 500-700 r / min and 35-40 DEG C for 2.5-3.5 h, the product was filtered, the precipitate was washed with distilled water and anhydrous ethanol alternately for 2-3 times, and dried at 60-70 DEG C for 2.5-3.5 h, and the antioxidant PAO@SMA microcapsules were obtained.

9. A method for preparing an anti-aging ABS composite material for a reflector according to claim 8, characterized in that, The usage ratio of the SMA, antioxidant PAO, dichloromethane, gelatin, sodium dodecyl sulfate and deionized water is 2-4 g:3-9 g:60-100 mL:3.2-4.8 g:0.3-0.5 g:160-240 mL.

10. An anti-aging ABS composite material for a light reflecting cover, characterized by, Prepared by the preparation method of any one of claims 1-9.