A corrosion-resistant PMMA / ABS composite material and its preparation method

Abstract

This invention provides a corrosion-resistant PMMA / ABS composite material and its preparation method, relating to the field of polymer materials technology. The composite material provided by this invention comprises, by weight, 50-80 parts PMMA matrix, 40-80 parts ABS matrix, 5-10 parts brominated flame retardant, 5-10 parts toughening agent, 2-5 parts compatibilizer, 0.1-1 part lubricant, 0.1-1 part antioxidant, 0.1-1 part weathering agent, and 3-5 parts corrosion-resistant filler; wherein the corrosion-resistant filler includes nano-modified silica and nano-modified antimony pentoxide. The composite material provided by this invention exhibits excellent acid and alkali corrosion resistance and good mechanical properties, while the flame-retardant performance is improved by combining nano-modified antimony pentoxide with the brominated flame retardant.

Description

Technical Field

[0001] This invention relates to the field of polymer materials technology, and in particular to a corrosion-resistant PMMA / ABS composite material and its preparation method. Background Technology

[0002] Polymethyl methacrylate (PMMA) is a thermoplastic. The ester side chains in its molecular structure endow the material with excellent light transmittance, good weather resistance, and insulation. PMMA also has high hardness, strong scratch resistance, and good chemical stability. However, PMMA is relatively brittle and has low impact resistance, making it prone to cracking in high-temperature or highly polar solvent environments. Acrylonitrile-butadiene-styrene copolymer (ABS) is another commonly used thermoplastic, formed by copolymerizing acrylonitrile, butadiene, and styrene. This structure allows ABS to combine the chemical resistance and hardness of acrylonitrile, the toughness and low-temperature toughness of butadiene, and the processability and surface gloss of styrene.

[0003] In existing technologies, PMMA and ABS are physically blended or modified by compatibilizers. The resulting composite material combines the performance advantages of both materials. For example, in terms of mechanical properties, PMMA can effectively improve the surface hardness, stiffness, and scratch resistance of the composite material, while the butadiene component in ABS can act as a toughening agent to significantly improve the brittleness of PMMA, thereby improving the impact resistance and toughness of the composite material. In addition, PMMA / ABS composite material can inherit the good thermoforming process flow of ABS, which can improve the defects of high processing temperature and high melt viscosity of pure PMMA. Furthermore, the excellent UV aging resistance of PMMA can, to some extent, compensate for the insufficient weather resistance of ABS material, and help delay the yellowing process of the composite material when used outdoors.

[0004] However, the corrosion resistance of PMMA / ABS composites in complex chemical environments remains a significant weakness. This is because the ester bonds in the PMMA molecular chain are prone to hydrolysis, degradation, or swelling in polar solvents, and the butadiene structure in ABS is susceptible to corrosion by oxidizing media and oil components, leading to softening, dissolution, or even cracking of the composite material. Furthermore, the interface between the ABS and PMMA phases in the composite material is easily penetrated and diffused by corrosive media, thus shortening the overall service life of the composite material and greatly restricting its application. Therefore, there is an urgent need to provide a solution to improve these problems. Summary of the Invention

[0005] The purpose of this invention is to provide a corrosion-resistant PMMA / ABS composite material and its preparation method, which has excellent acid and alkali corrosion resistance and good mechanical properties. At the same time, the flame retardant performance can be improved by combining nano-modified antimony pentoxide with a bromine-based flame retardant.

[0006] In a first aspect, the present invention provides a corrosion-resistant PMMA / ABS composite material, comprising, by weight: 50-80 parts PMMA matrix, 40-80 parts ABS matrix, 5-10 parts brominated flame retardant, 5-10 parts toughening agent, 2-5 parts compatibilizer, 0.1-1 part lubricant, 0.1-1 part antioxidant, 0.1-1 part weathering agent, and 3-5 parts corrosion-resistant filler; wherein the corrosion-resistant filler comprises nano-modified silica and nano-modified antimony pentoxide.

[0007] Optionally, the particle size of the nanoscale modified silica and the nanoscale modified antimony pentoxide are independently between 10 nm and 200 nm.

[0008] Optionally, the mass ratio of the nanoscale modified silica to the nanoscale modified antimony pentoxide is 1:(0.5-2).

[0009] Optionally, the corrosion-resistant filler further includes polymeric wax coating the surfaces of the nano-modified silica and the nano-modified antimony pentoxide.

[0010] Optionally, the preparation method of the nanoscale modified silica includes: ultrasonically dispersing fumed silica in anhydrous ethanol to obtain a silica suspension; adding silane hydrolysate dropwise to the silica suspension at 50℃-60℃, mixing, and then refluxing at 70℃-80℃ for 4h-6h before centrifugation to obtain activated silica; and washing the activated silica with anhydrous ethanol and drying it to obtain nanoscale modified silica.

[0011] Optionally, the specific surface area of ​​the fumed silica is 150 m². 2 / g-200m 2 / g.

[0012] Optionally, the solid content of the silica suspension is 5%-15%.

[0013] Optionally, the concentration of silane solute in the silane hydrolysate is 3%-8%.

[0014] Optionally, the silane solute in the silane hydrolysate includes one of KH550 and KH560.

[0015] Optionally, the mass ratio of the fumed silica to the silane solute in the silane hydrolysate is 1:(0.02-0.05).

[0016] Optionally, the preparation method of the nano-scale modified antimony pentoxide includes: ultrasonically dispersing nano-scale antimony pentoxide in deionized water to obtain antimony pentoxide slurry; mixing sodium stearate solution with antimony pentoxide slurry with pH 9-10, and then refluxing at 70℃-80℃ for 2h-3h to obtain mixed slurry; adjusting the pH of the mixed slurry to 6-7, centrifuging, washing, and drying to obtain nano-scale modified antimony pentoxide.

[0017] Optionally, the solid content of the antimony pentoxide slurry is 10%-15%.

[0018] Optionally, the mass ratio of sodium stearate to nano-sized antimony pentoxide in the sodium stearate solution is (0.03-0.07):1.

[0019] Optionally, antimony pentoxide nano-sized particles and titanate coupling agent are ultrasonically dispersed in deionized water to obtain antimony pentoxide slurry.

[0020] Optionally, the mass ratio of the titanate coupling agent to the nano-sized antimony pentoxide is (0.02-0.03):1.

[0021] Optionally, the preparation method of the corrosion-resistant filler includes: dispersing nano-modified silica and nano-modified antimony pentoxide in deionized water and spray drying to obtain a mixed filler; mixing the mixed filler with polymerized wax at a mass ratio of 1:(0.03-0.08), stirring and mixing in an environment 5℃-10℃ higher than the melting point of the polymerized wax, cooling and dispersing, and sieving to obtain the corrosion-resistant filler.

[0022] Optionally, the polymerized wax is an ethylene-vinyl acetate copolymer wax.

[0023] Optionally, the PMMA matrix includes one of Samsung TF-0956 and Samsung TF-0959.

[0024] Optionally, the ABS matrix includes Chi Mei PA-758.

[0025] Optionally, the toughening agent comprises high-polymer powder.

[0026] Optionally, the compatibilizer includes a maleic anhydride-styrene copolymer.

[0027] Optionally, the lubricant includes one of zinc stearate, polyethylene wax, and polytetrafluoroethylene.

[0028] Optionally, the antioxidant includes one of antioxidant 1010, antioxidant 1076, and antioxidant 168.

[0029] Optionally, the weathering agent includes one of light stabilizer 770 and light stabilizer 234.

[0030] Secondly, the present invention also provides a method for preparing any of the above-mentioned optional composite materials, comprising: mixing PMMA matrix, ABS matrix, brominated flame retardant, toughening agent, compatibilizer, lubricant, antioxidant, weathering agent, and corrosion-resistant filler in a high-speed mixer to obtain a preliminary mixture; and melting-extruding and granulating the preliminary mixture in a twin-screw extruder to obtain a corrosion-resistant PMMA / ABS composite material.

[0031] Optionally, the temperature in the twin-screw extruder is 180℃-210℃ in zone 1, 220℃-240℃ in zone 2, 220℃-240℃ in zone 3, 200℃-230℃ in zone 4, 200℃-230℃ in zone 5, 210℃-240℃ in zone 6, 210℃-240℃ in zone 7, and 210℃-240℃ in zone 8; the screw speed of the twin-screw extruder is 300rpm-400rpm.

[0032] The corrosion-resistant PMMA / ABS composite material provided by this invention has at least one of the following beneficial technical effects compared with the prior art: 1. By adding nano-modified silica and nano-modified antimony pentoxide composite as corrosion-resistant fillers to PMMA / ABS composite materials, the mechanical properties and strength of the composite materials can be improved. At the same time, it can also effectively extend the corrosion diffusion path of corrosive media in the composite materials, thereby improving the corrosion resistance of the composite materials in acid and alkali environments, and effectively improving the durability and performance stability of the composite materials in acid and alkali environments. 2. By coating the surfaces of nano-modified silica and nano-modified antimony pentoxide with polymer wax, the flowability and dispersibility of corrosion-resistant fillers in the blending process of composite materials can be effectively improved. This helps the corrosion-resistant fillers form a stable and continuous filling network in the composite materials. At the same time, the polymer wax can also enhance the compatibility between the corrosion-resistant fillers and the PMMA matrix and ABS matrix, thereby improving the interfacial bonding strength. Detailed Implementation

[0033] To make the objectives, technical solutions, and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below. Obviously, the described embodiments are only some embodiments of the present invention, not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention. Unless otherwise defined, the technical or scientific terms used herein should have the ordinary meaning understood by those skilled in the art to which this invention pertains.

[0034] This invention provides a corrosion-resistant PMMA / ABS composite material, comprising, by weight: 50-80 parts PMMA matrix, 40-80 parts ABS matrix, 5-10 parts brominated flame retardant, 5-10 parts toughening agent, 2-5 parts compatibilizer, 0.1-1 part lubricant, 0.1-1 part antioxidant, 0.1-1 part weathering agent, and 3-5 parts corrosion-resistant filler. In practice, by using PMMA and ABS matrices as matrix materials to create the composite material, the PMMA matrix improves the structural strength and weather resistance of the composite material, while the ABS matrix improves its impact resistance and surface gloss.

[0035] Furthermore, adding compatibilizers to composite materials can improve the compatibility between the PMMA matrix and the ABS matrix, preventing phase separation during blending and improving the bonding stability between the PMMA and ABS matrices. Simultaneously, the addition of toughening agents can improve the toughness and structural stability of the composite material, while lubricants can improve the flowability of the composite material during processing, thereby improving the surface finish and reducing internal defects during molding. In fact, adding antioxidants, weathering agents, and brominated flame retardants to composite materials can respectively improve oxidation resistance, weather resistance, and flame retardancy.

[0036] Specifically, the corrosion-resistant fillers include nano-modified silica and nano-modified antimony pentoxide. In fact, the nano-sized corrosion-resistant fillers are uniformly dispersed in the composite material and effectively extend and tortuous the corrosion path of the corrosive medium, thereby improving the corrosion resistance of the composite material. Furthermore, the dispersion of the fillers in the composite material can further improve its mechanical properties and strength, making the composite material more dense. At the same time, antimony pentoxide can synergistically work with brominated flame retardants to further improve the flame-retardant properties of the composite material.

[0037] In some embodiments, the particle sizes of the nano-modified silica and modified antimony pentoxide used in the composite material are independently 10 nm to 200 nm. In fact, dispersing small-particle-size corrosion-resistant fillers in the composite material helps to achieve uniform dispersion of the corrosion-resistant filler during the blending process. Furthermore, after the composite material is molded, the corrosion-resistant filler can fully fill the composite material to form a filler network, thereby reducing the pathways for corrosive media to penetrate the composite material and thus improving its corrosion resistance. Further, the mass ratio of nano-modified silica to nano-modified antimony pentoxide is 1:(0.5-2).

[0038] In some embodiments, the corrosion-resistant filler used in the composite material further includes a polymeric wax coating the surfaces of the nano-modified silica and the nano-modified antimony pentoxide. In fact, the surface polymeric wax can improve the consistency of the nano-modified silica and nano-modified antimony pentoxide in the corrosion-resistant filler, thereby contributing to the uniform dispersion of the corrosion-resistant filler in the composite material during blending. Simultaneously, the polymeric wax can also improve the compatibility of the filler in the composite material. Specifically, the polymeric wax is an ethylene-vinyl acetate copolymer wax.

[0039] In some embodiments, the preparation method of the corrosion-resistant filler includes: dispersing nano-modified silica and nano-modified antimony pentoxide in deionized water and then spray-drying to obtain a mixed filler; mixing the mixed filler with polymeric wax at a mass ratio of 1:(0.03-0.08), stirring and mixing in an environment 5°C-10°C higher than the melting point of the polymeric wax, cooling, dispersing, and sieving to obtain the corrosion-resistant filler. In fact, spray drying can uniformly disperse nano-modified silica and nano-modified antimony pentoxide, and stirring and mixing in the molten polymer can uniformly coat the filler surface, forming a corrosion-resistant filler with a uniform surface and good flowability.

[0040] In some embodiments, the preparation method of nanoscale modified silica includes: ultrasonically dispersing fumed silica in anhydrous ethanol to obtain a silica suspension; adding silane hydrolysate dropwise to the silica suspension at 50℃-60℃, mixing, and then refluxing at 70℃-80℃ for 4-6 hours, followed by centrifugation to obtain activated silica; washing the activated silica with anhydrous ethanol and drying it to obtain nanoscale modified silica. Specifically, the solid content of fumed silica in the silica suspension is 5%-15%, and the concentration of silane solute in the silane hydrolysate is 3%-8%.

[0041] In some embodiments, when preparing nanoscale modified silica, the silane solute in the silane hydrolysate includes one of KH550 and KH560, and the mass ratio of fumed silica to silane solute is 1:(0.02-0.05). This facilitates uniform activation treatment of the fumed silica surface by the silane solute and helps maintain good dispersibility of the fumed silica during silane activation treatment, avoiding agglomeration and sedimentation of the fumed silica.

[0042] In some further embodiments, the specific surface area of ​​fumed silica can be 150 m². 2 / g-200m 2 / g. By treating the surface of fumed silica with silane, silane active groups can be grafted onto the surface of fumed silica, which is beneficial to improving the reactivity of the fumed silica surface, thereby improving the dispersion uniformity of nanoscale modified silica in the composite material, and at the same time helping to uniformly coat the polymer wax on the surface of nanoscale modified silica.

[0043] In some embodiments, the preparation method of nanoscale modified antimony pentoxide includes: ultrasonically dispersing nanoscale antimony pentoxide in deionized water to obtain an antimony pentoxide slurry; mixing sodium stearate solution with the antimony pentoxide slurry at pH 9-10, and then refluxing at 70℃-80℃ for 2-3 hours to obtain a mixed slurry; adjusting the pH of the mixed slurry to 6-7, centrifuging, washing, and drying to obtain nanoscale modified antimony pentoxide. In fact, the refluxing process helps sodium stearate to be uniformly dispersed on the surface of antimony pentoxide, and then, during the pH change of the mixed slurry, sodium stearate reacts to generate stearic acid, which coats the surface of the nanoscale antimony pentoxide, thus forming a stearic acid coating layer. This helps improve the compatibility of nanoscale antimony pentoxide with polymerized wax.

[0044] In some further embodiments, the solid content of nano-sized antimony pentoxide in the antimony pentoxide slurry is 10%-15%, and the mass ratio of sodium stearate to nano-sized antimony pentoxide in the sodium stearate solution can be (0.03-0.07):1. In fact, by adjusting the mass ratio of sodium stearate to nano-sized antimony pentoxide, the coating thickness of stearic acid on nano-sized antimony pentoxide can be adjusted. In other embodiments, nano-sized antimony pentoxide and a titanate coupling agent can be ultrasonically dispersed in deionized water to obtain an antimony pentoxide slurry. The stability of the antimony pentoxide slurry can be improved by the activation effect of the titanate coupling agent on the surface of the nano-sized antimony pentoxide. Specifically, the mass ratio of titanate coupling agent to nano-sized antimony pentoxide is (0.02-0.03):1.

[0045] In some embodiments, the PMMA matrix used in the composite material includes one of Samsung TF-0956 and Samsung TF-0959, the ABS matrix includes Chi Mei PA-758, the toughening agent includes high-rubber powder, the compatibilizer includes maleic anhydride-styrene copolymer, the lubricant includes one of zinc stearate, polyethylene wax, and polytetrafluoroethylene, the antioxidant includes one of antioxidant 1010, antioxidant 1076, and antioxidant 168, the weathering agent includes one of light stabilizer 770 and light stabilizer 234, and the brominated flame retardant includes one of decabromodiphenyl ether, decabromodiphenyl ethane, and bromophenol.

[0046] This invention also provides a method for preparing the corrosion-resistant PMMA / ABS composite material in any of the above embodiments, comprising: mixing PMMA matrix, ABS matrix, brominated flame retardant, toughening agent, compatibilizer, lubricant, antioxidant, weathering agent, and corrosion-resistant filler in a high-speed mixer to obtain a preliminary mixture; and melting-extruding and granulating the preliminary mixture in a twin-screw extruder to obtain the corrosion-resistant PMMA / ABS composite material. Specifically, the temperature in the twin-screw extruder is 180℃-210℃ in zone 1, 220℃-240℃ in zone 2, 220℃-240℃ in zone 3, 200℃-230℃ in zone 4, 200℃-230℃ in zone 5, 210℃-240℃ in zone 6, 210℃-240℃ in zone 7, and 210℃-240℃ in zone 8; and the screw speed of the twin-screw extruder is 300rpm-400rpm.

[0047] Preparation Example 1 Example 1 provides a method for preparing nanoscale modified silica, comprising the following steps: Z1. Use deionized water to treat fumed silica (purchased from Shenzhen Huiya New Materials Technology Co., Ltd., brand name Evonik AEROSIL 200, specific surface area 200m²). 2 After being rinsed and dried to constant weight, the dried fumed silica (with an average particle size of 12 nm) was ultrasonically dispersed in anhydrous ethanol at an ultrasonic power of 200 W to obtain a silica suspension with a solid content of 10%. Z2. Dissolve KH550 in a 50 vol.% ethanol aqueous solution to prepare a 5% silane hydrolysate. Add the silane hydrolysate dropwise to the silica suspension while maintaining the reflux reaction at 50°C during the addition process. Control the mass ratio of KH550 to fumed silica to be 0.03:1. After the addition is completed, raise the temperature to 75°C and reflux for 5 hours. Z3. After the reflux reaction is completed, activated silica is obtained by centrifugation at 800 rpm. The activated silica is then rinsed with anhydrous ethanol and dried at 70°C to constant weight to obtain nano-sized modified silica.

[0048] Preparation Example 2 Example 2 provides a method for preparing nanoscale modified antimony pentoxide, comprising the following steps: Z1. Nano-sized antimony pentoxide (purchased from Wuhan Jiyesheng Chemical Co., Ltd., with an average particle size of 100nm) was ultrasonically dispersed in deionized water at an ultrasonic power of 200W, and a 5% sodium hydroxide aqueous solution was added to adjust the pH to 10 and the solid content to 10% to obtain an antimony pentoxide slurry. Z2. Mix the sodium stearate solution with the antimony pentoxide slurry prepared in Z1, and control the mass ratio of sodium stearate to nano-sized antimony pentoxide in the mixed system to be 0.05:1. Then, reflux the mixture at 75℃ and 300rpm for 3h to obtain the mixed slurry. Z3. After adjusting the pH of the mixed slurry to 7 with dilute hydrochloric acid, centrifuge at 800 rpm, rinse with deionized water, and dry at 80°C to constant weight to obtain nano-sized modified antimony pentoxide.

[0049] Preparation Example 3 Preparation Example 3 provides a method for preparing nano-sized modified antimony pentoxide. The difference from Preparation Example 2 is that in step Z1, nano-sized antimony pentoxide and titanate coupling agent KR-238S are mixed at a mass ratio of 1:0.03 and added to a 50 vol.% ethanol aqueous solution for ultrasonic dispersion. Then, a 5% sodium hydroxide aqueous solution is added to adjust the pH to 10 and the solid content to 10% to obtain an antimony pentoxide slurry.

[0050] Preparation Example 4 Example 4 of this preparation provides a method for preparing a corrosion-resistant filler, including the following steps: S1. The nano-sized modified silica prepared in Preparation Example 1 and the nano-sized modified antimony pentoxide prepared in Preparation Example 2 are mixed in a mass ratio of 1:1 and added to deionized water. After ultrasonic dispersion, a mixed suspension with a solid content of 10% is obtained. The mixed filler is obtained by spray drying the mixed suspension. S2. The mixed filler and ethylene-vinyl acetate copolymer wax (purchased from Shanghai Oushuo Plastics Co., Ltd., brand name Dow ELVAX 760) were mixed at a mass ratio of 1:0.05. The mixture was kept at 120°C in a nitrogen atmosphere for 30 minutes until the ethylene-vinyl acetate copolymer wax was completely melted. The mixture was then stirred at 300 rpm. After cooling to room temperature, the bonded materials were broken up by stirring and then sieved to obtain the corrosion-resistant filler.

[0051] Preparation Example 5 Preparation Example 5 provides a method for preparing a corrosion-resistant filler. The difference from Preparation Example 4 is that in step S1, the nano-modified silica prepared in Preparation Example 1 and the nano-modified antimony pentoxide prepared in Preparation Example 3 are mixed in deionized water at a mass ratio of 1:1.

[0052] Preparation Example 6 Preparation Example 6 provides a method for preparing a corrosion-resistant filler. The difference from Preparation Example 4 is that in step S1, the nano-sized modified silica obtained in Preparation Example 1 and nano-sized antimony pentoxide (purchased from Wuhan Jiyesheng Chemical Co., Ltd., with an average particle size of 100 nm) are mixed in a 1:1 mass ratio and added to deionized water.

[0053] Preparation Example 7 Preparation Example 7 provides a method for preparing a corrosion-resistant filler, which differs from Preparation Example 4 in that, in step S1, fumed silica (purchased from Shenzhen Huiya New Materials Technology Co., Ltd., brand name Evonik AEROSIL 200, with a specific surface area of ​​200 m²) is added. 2 The nano-modified antimony pentoxide (with an average particle size of 12 nm) prepared in Preparation Example 2 was mixed with deionized water at a mass ratio of 1:1.

[0054] Preparation Example 8 Preparation Example 8 provides a method for preparing a corrosion-resistant filler, which differs from Preparation Example 4 in that, in step S1, fumed silica (purchased from Shenzhen Huiya New Materials Technology Co., Ltd., brand name Evonik AEROSIL 200, with a specific surface area of ​​200 m²) is added. 2 / g, with an average particle size of 12nm) and nano-sized antimony pentoxide (purchased from Wuhan Jiyesheng Chemical Co., Ltd., with an average particle size of 100nm) were mixed in a 1:1 mass ratio and added to deionized water.

[0055] Preparation Example 9 This preparation example provides a method for preparing corrosion-resistant filler. The difference from preparation example 4 is that step S2 is not performed. The mixed filler obtained in step S1 is the corrosion-resistant filler.

[0056] Examples 1 to 4 Examples 1 to 4 provide a corrosion-resistant PMMA / ABS composite material, wherein the amount of each component is shown in Table 1 below.

[0057] Table 1. Components and dosages of the composite materials in Examples 1 to 4

[0058] In Examples 1 to 4, the PMMA matrix used was Samsung TF-0956, the ABS matrix used was Chi Mei PA-758, the toughening agent used was high-rubber powder HR-181 purchased from Dongguan Chuangshi Plastic Raw Materials Co., Ltd., the compatibilizer used was maleic anhydride-styrene copolymer SMA1000 purchased from Greenlink (Jining) Chemical Technology Co., Ltd., the lubricant used was polyethylene wax, the antioxidant used was antioxidant 1010 and antioxidant 1076 in a 1:1 mass ratio, and the weathering agent used was light stabilizer 770 and light stabilizer 234 in a 1:1 mass ratio. The corrosion-resistant filler used in Examples 1 to 3 was the corrosion-resistant filler obtained in Preparation Example 4, and the corrosion-resistant filler used in Example 4 was the corrosion-resistant filler obtained in Preparation Example 5.

[0059] Comparative Examples 1 to 4 Comparative Examples 1 to 4 provide a corrosion-resistant PMMA / ABS composite material, which differs from Example 3 in that the corrosion-resistant fillers used in Comparative Examples 1 to 4 are the corrosion-resistant fillers prepared in Preparation Examples 6 to 9, respectively.

[0060] Comparative Example 5 Comparative Example 5 provides a corrosion-resistant PMMA / ABS composite material, which differs from Example 3 in that the corrosion-resistant filler used is an equal amount of fumed silica (purchased from Shenzhen Huiya New Material Technology Co., Ltd., brand name Evonik AEROSIL 200, with a specific surface area of ​​200 m²). 2 / g, with an average particle size of 12nm).

[0061] Comparative Example 6 Comparative Example 6 provides a corrosion-resistant PMMA / ABS composite material. The difference from Example 3 is that the corrosion-resistant filler used is an equal amount of nano-sized antimony pentoxide (purchased from Wuhan Jiyesheng Chemical Co., Ltd., with an average particle size of 100 nm).

[0062] The preparation methods of the corrosion-resistant PMMA / ABS composite materials in Examples 1 to 4 and Comparative Examples 1 to 6 are as follows: the raw materials are mixed in a high-speed mixer to obtain a preliminary mixture, and then the preliminary mixture is added to the feeding hopper of a twin-screw extruder. The screw speed of the twin-screw extruder is set to 300 rpm, and the temperatures of zones one to eight are 200℃, 230℃, 230℃, 220℃, 220℃, 220℃, 210℃, and 210℃, respectively. The corrosion-resistant PMMA / ABS composite material is obtained by extrusion and granulation in the twin-screw extruder.

[0063] Performance testing The tensile strength of the composite materials in Examples 1, 4, and Comparative Examples 1 to 6 was tested using the standard described in ASTM D638; the flexural strength of the composite materials in Examples 1, 4, and Comparative Examples 1 to 6 was tested using the standard described in ASTM D790; and the notched impact strength of the composite materials in Examples 1, 4, and Comparative Examples 1 to 6 was tested using the standard described in ASTM D256. Three sets of experiments were conducted for each set of experiments, and the average value was calculated. The test results are shown in Table 2 below.

[0064] The flame retardant properties of the composite materials in Examples 1, 4, and Comparative Examples 1 to 6 were tested using the standards described in UL-94, and the results are shown in Table 2 below. The composite materials in Examples 1, 4, and Comparative Examples 1 to 6 were immersed in 98% sulfuric acid (acid) and saturated sodium hydroxide solution (alkali) for 7 days, respectively. The retention rates of tensile strength, flexural strength, and impact strength after corrosion were tested according to the above method, compared to before corrosion, and the results are shown in Table 3 below; where, retention rate (%) = A / B × 100%, A is the performance test value of the composite material after corrosion, and B is the performance test value of the composite material before corrosion.

[0065] Table 2 Performance test data of corrosion-resistant PMMA / ABS composite materials

[0066] Table 3. Performance retention rate of corrosion-resistant PMMA / ABS composite materials after corrosion.

[0067] As can be seen from the data in Tables 2 and 3, the corrosion-resistant PMMA / ABS composite material provided by this invention possesses good mechanical properties and strength. Furthermore, it maintains good performance even after immersion in acid and alkaline solutions, indicating its excellent corrosion resistance. Examples 1 and Comparative Examples 1 to 3 demonstrate that surface modification treatment with fumed silica and nano-sized antimony pentoxide effectively improves the interfacial bonding performance of the corrosion-resistant filler in the composite material, thereby affecting the mechanical properties and strength of the composite material. Examples 1 and 4 show that coating the surface of the corrosion-resistant filler with a layer of polymeric wax effectively enhances the compatibility of the corrosion-resistant filler in the composite material.

[0068] While embodiments of the present invention have been described in detail above, it will be apparent to those skilled in the art that various modifications and variations can be made to these embodiments. However, it should be understood that such modifications and variations fall within the scope and spirit of the invention as set forth in the claims. Furthermore, the invention described herein may have other embodiments and can be implemented or carried out in various ways.

Claims

1. A corrosion-resistant PMMA / ABS composite material, characterized in that, The product comprises, by weight, 50-80 parts PMMA matrix, 40-80 parts ABS matrix, 5-10 parts brominated flame retardant, 5-10 parts toughening agent, 2-5 parts compatibilizer, 0.1-1 part lubricant, 0.1-1 part antioxidant, 0.1-1 part weathering agent, and 3-5 parts corrosion-resistant filler; wherein the corrosion-resistant filler comprises nano-modified silica and nano-modified antimony pentoxide.

2. The composite material according to claim 1, characterized in that: The particle sizes of the nano-modified silica and the nano-modified antimony pentoxide are independently 10nm-200nm; and / or, the mass ratio of the nano-modified silica to the nano-modified antimony pentoxide is 1:(0.5-2); and / or, the corrosion-resistant filler further includes polymeric wax coating the surfaces of the nano-modified silica and the nano-modified antimony pentoxide.

3. The composite material according to claim 1 or 2, characterized in that: The preparation method of the nanoscale modified silica includes: ultrasonically dispersing fumed silica in anhydrous ethanol to obtain a silica suspension; adding silane hydrolysate dropwise to the silica suspension at 50℃-60℃, mixing, and then refluxing at 70℃-80℃ for 4h-6h before centrifugation to obtain activated silica; washing the activated silica with anhydrous ethanol and drying it to obtain nanoscale modified silica.

4. The composite material according to claim 3, characterized in that: The specific surface area of ​​the fumed silica is 150 m². 2 / g-200m 2 / g; and / or, the solid content of the silica suspension is 5%-15%; and / or, the concentration of silane solute in the silane hydrolysate is 3%-8%; and / or, the silane solute in the silane hydrolysate includes one of KH550 and KH560; and / or, the mass ratio of the fumed silica to the silane solute in the silane hydrolysate is 1:(0.02-0.05).

5. The composite material according to claim 1 or 2, characterized in that: The preparation method of the nano-scale modified antimony pentoxide includes: ultrasonically dispersing nano-scale antimony pentoxide in deionized water to obtain antimony pentoxide slurry; mixing sodium stearate solution with antimony pentoxide slurry with pH 9-10, and then refluxing at 70℃-80℃ for 2h-3h to obtain mixed slurry; adjusting the pH of the mixed slurry to 6-7, centrifuging, washing, and drying to obtain nano-scale modified antimony pentoxide.

6. The composite material according to claim 5, characterized in that: The solid content of the antimony pentoxide slurry is 10%-15%; and / or, the mass ratio of sodium stearate to the nano-sized antimony pentoxide in the sodium stearate solution is (0.03-0.07):1; and / or, the antimony pentoxide slurry is obtained by ultrasonically dispersing nano-sized antimony pentoxide and titanate coupling agent in deionized water, wherein the mass ratio of the titanate coupling agent to the nano-sized antimony pentoxide is (0.02-0.03):

1.

7. The composite material according to claim 1, characterized in that: The preparation method of the corrosion-resistant filler includes: dispersing nano-modified silica and nano-modified antimony pentoxide in deionized water and then spray drying to obtain a mixed filler; mixing the mixed filler with polymeric wax at a mass ratio of 1:(0.03-0.08), stirring and mixing in an environment 5℃-10℃ higher than the melting point of the polymeric wax, cooling and dispersing, and sieving to obtain the corrosion-resistant filler; wherein: the polymeric wax is ethylene-vinyl acetate copolymer wax.

8. The composite material according to claim 1, characterized in that: The PMMA matrix includes one of Samsung TF-0956 and Samsung TF-0959; and / or, the ABS matrix includes Chi Mei PA-758; and / or, the toughening agent includes high-resin powder; and / or, the compatibilizer includes maleic anhydride-styrene copolymer; and / or, the lubricant includes one of zinc stearate, polyethylene wax, and polytetrafluoroethylene; and / or, the antioxidant includes one of antioxidant 1010, antioxidant 1076, and antioxidant 168; and / or, the weathering agent includes one of light stabilizer 770 and light stabilizer 234.

9. A method for preparing the composite material according to any one of claims 1 to 8, characterized in that, include: A primary mixture is prepared by mixing PMMA matrix, ABS matrix, brominated flame retardant, toughening agent, compatibilizer, lubricant, antioxidant, weathering agent, and corrosion-resistant filler in a high-speed mixer; the primary mixture is then melt-extruded and granulated in a twin-screw extruder to obtain a corrosion-resistant PMMA / ABS composite material.

10. The preparation method according to claim 9, characterized in that, The twin-screw extruder has the following temperature zones: Zone 1: 180℃-210℃; Zone 2: 220℃-240℃; Zone 3: 220℃-240℃; Zone 4: 200℃-230℃; Zone 5: 200℃-230℃; Zone 6: 210℃-240℃; Zone 7: 210℃-240℃; Zone 8: 210℃-240℃; and the screw speed is 300 rpm-400 rpm.

Images