Anti-aging PMMA / ASA plastic alloy and preparation method thereof

Abstract

The invention discloses an anti-aging PMMA / ASA plastic alloy and a preparation method thereof, and belongs to the technical field of plastic alloys. The anti-aging PMMA / ASA plastic alloy is prepared from the following raw material components in percentage by mass: 50 to 70 percent of PMMA resin, 10 to 20 percent of ASA resin, 4 to 6 percent of toughening agent B, 10 to 20 percent of toughening agent A, 2 to 5 percent of compatilizer, 0.2 to 0.5 percent of antioxidant aid, 0.1 to 0.5 percent of lubricant, 0.2 to 0.5 percent of precipitation-resistant aid, 0.5 to 1 percent of light aging-resistant aid, 0.5 to 1 percent of toner and 0.5 to 1 percent of carbon black. The prepared PMMA / ASA plastic alloy not only has high gloss and scratch resistance of PMMA and weather resistance of ASA, but also can reduce precipitation of small molecules, so that the mold wiping period in actual injection molding production is shortened, the PMMA / ASA plastic alloy has very high heat resistance, and an actual injection-molded product does not deform at a high temperature.

Description

Technical Field

[0001] The invention relates to an anti-aging PMMA / ASA plastic alloy and a preparation method thereof. Background Art

[0002] Polymethyl methacrylate (PMMA), an important transparent thermoplastic engineering plastic, offers excellent optical properties, high surface gloss, and scratch resistance, making it widely used in automotive applications such as headlight covers and signage. However, PMMA's poor toughness and impact resistance limit its application in structural parts requiring high mechanical properties.

[0003] To improve the mechanical properties of PMMA, it is often blended with acrylonitrile-styrene-acrylate copolymer (ASA), which has excellent impact resistance and weather resistance. ASA resin, as a terpolymer of acrylonitrile, styrene, and acrylate, not only has good impact resistance, but also exhibits excellent weather resistance, coloring, and chemical resistance due to the presence of acrylonitrile. It is widely used in automotive exterior parts such as grilles, triangle blocks, and pillar panels. However, due to the large difference in polarity between PMMA and ASA, the compatibility between the two is poor, which can easily lead to phase separation and weak interfacial bonding in the blend system, which in turn causes defects such as material delamination and decreased mechanical properties, seriously affecting its actual use effect.

[0004] To solve the above problems, relevant patents have attempted to improve the compatibility between PMMA and ASA by introducing a compatibilizer. For example, patent CN201610414293.7 discloses a PMMA / ASA alloy resin composition prepared using compatibilizers such as MMA-SAN, SMA or AS-g-MAH, which effectively improves the compatibility between the two, so that the resulting material exhibits good performance in mechanical properties, hardness, heat resistance and aging resistance, and realizes direct injection molding without spraying. Patent CN202110826631.9 further developed a heat-resistant compatibilizer based on styrene-methyl methacrylate-maleic anhydride terpolymer and tetrapolymer, which significantly improved the thermal oxygen stability and heat resistance temperature of the material, while optimizing the dispersion of the black masterbatch in the matrix, reducing the incidence of appearance defects such as silver wire, and meeting the demand for "black and bright" products. In addition, patent CN201510982727.9 successfully prepared a PMMA / ASA alloy resin composition with high gloss, excellent mechanical properties and spray-free characteristics by introducing a toughening agent and a compatibilizer for synergistic effect.

[0005] While existing technologies have made some progress in improving the compatibility and overall performance of PMMA / ASA alloys, numerous challenges remain in actual production. First, some compatibilizers or additives can easily release small molecules during high-temperature injection molding, causing frequent mold contamination and requiring frequent cleaning, impacting production efficiency. Second, PMMA / ASA materials used in optical components such as headlights and rearview mirrors are prone to light diffusion due to phase separation or additive precipitation, affecting light transmission uniformity and posing potential safety risks.

[0006] Therefore, there is an urgent need to develop an aging-resistant PMMA / ASA plastic alloy and its preparation method, which can not only effectively improve the compatibility between PMMA and ASA, improve the toughness and impact resistance of the material, but also take into account the process stability and optical properties of the material during the injection molding process to meet the automotive industry's growing demand for high-performance and high-reliability materials. Summary of the Invention

[0007] The purpose of the present invention is to provide an anti-aging PMMA / ASA plastic alloy and a preparation method thereof, so as to solve the technical problems mentioned in the above background technology.

[0008] The technical solution for achieving the purpose of the present invention is: In a first aspect, the present invention provides an anti-aging PMMA / ASA plastic alloy, which comprises, by mass, 50-70% PMMA resin, 10-20% ASA resin, 4-6% toughening agent B, 10-20% toughening agent A, 2%-5% compatibilizer, 0.2-0.5% antioxidant, 0.1-0.5% lubricant, 0.2-0.5% anti-precipitation agent, 0.5-1% light aging resistance agent, 0.5-1% color powder, and 0.5-1% carbon black.

[0009] The PMMA resin has a melt index of 1-10 g / 10 min under the test conditions of 230° C. and 3.8 kg, and a Vicat softening temperature of 95-110° C. under the test conditions of 50° C. / hr and 50 N.

[0010] The ASA resin has a melt index of 15-30 g / 10 min under 220° C. and 10 kg test conditions, and a Vicat softening temperature of 100-110° C. under 50° C. / hr and 50 N test conditions.

[0011] The compatibilizer is a styrene-maleic anhydride copolymer, the melt index of which is 1-8 g / 10 min under the test conditions of 230° C. and 2.16 kg, and the heat deformation temperature of which is 110-130° C. under the test conditions of 1.8 MPa.

[0012] The antioxidant auxiliary agent is one or both of phosphite and pentaerythritol tetrakis[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate.

[0013] The lubricant is one or both of silicone and polyethylene wax.

[0014] The anti-precipitation agent is benzofuranone. Because polymer extrusion processing is typically performed in an oxygen-deficient state, high temperatures or shear forces generate a large amount of carbon radicals (R·) rather than alkoxy radicals (RO·) and hydroxyl radicals (·OH). Benzofuranone can effectively capture carbon radicals.

[0015] The light aging resistance auxiliary agent is one or both of 2-(2'-hydroxy-3',5'-bis(a,a-dimethylbenzyl)phenyl)benzotriazole and hindered amine light stabilizer.

[0016] The three primary organic dyes of pink, yellow and blue are mixed to make piano black toner.

[0017] The particle size of the carbon black is 15-30 nm, preferably 25 nm. Adding carbon black can effectively block the light source.

[0018] Furthermore, the toughening agent A includes, from the inside to the outside, a styrene-butadiene core layer, a silicone oil layer, and an acrylate block copolymer shell layer.

[0019] Furthermore, the acrylic ester block copolymer shell layer is obtained by copolymerization of acrylic ester, hydroxymethyl acrylamide and alkenyl cyanate.

[0020] Furthermore, the toughening agent B is ethylene-methyl acrylate-glycidyl methacrylate.

[0021] In a second aspect, the present invention provides a method for preparing an aging-resistant PMMA / ASA plastic alloy, comprising the following preparation steps: (1) Prepare the raw materials according to the following components and contents: PMMA resin 50~70%, ASA resin 10~20%, toughening agent B4~6%, toughening agent A10~20%, compatibilizer 2%~5%, antioxidant 0.2~0.5%, lubricant 0.1~0.5%, anti-precipitation agent 0.2~0.5%, light aging agent 0.5~1%, color powder 0.5~1%, carbon black 0.5~1%; (2) The PMMA resin, ASA resin, toughening agent B, toughening agent A, compatibilizer, antioxidant, lubricant, anti-precipitation agent, light aging agent, color powder, and carbon black prepared in step (1) were premixed in a high-speed mixer for 90 seconds, and then continued to mix at 50-110°C for 25-35 minutes; (3) The premixed material in step (2) is passed through a twin-screw extruder, melt-extruded at an extrusion temperature of 180-230° C. and a screw speed of 250 rpm, cooled and granulated to obtain an anti-aging PMMA / ASA plastic alloy.

[0022] Furthermore, the preparation steps of toughening agent A are as follows: A1. Styrene monomer, liquefied compressed butadiene monomer, deionized water, a water-soluble initiator, and an emulsifier are subjected to emulsion polymerization at a certain reaction temperature and under nitrogen for a period of time to obtain a non-polar core layer in a core-shell structure; A2. Add a certain amount of hydrogenated silicone oil to the prepared core layer. Under the action of a transition metal catalyst, the reaction is controlled at a certain temperature to cause addition of unsaturated double bonds in the core layer structure according to the coordination addition mechanism. The addition reaction time is controlled within a certain period of time to produce a silicone oil layer containing an organic silicon structure. A3. Acrylate, hydroxymethyl acrylamide, and alkenyl cyanate are added to the silicone oil layer containing an organosilicon structure. Unreacted hydrogen in the hydrogen-containing silicone oil dehydrogenates the hydroxyl groups in the hydroxymethyl acrylamide under the action of a transition metal catalyst; the acrylate monomer and alkenyl cyanate are subjected to an emulsion polymerization reaction to obtain a shell layer having polar groups. A4. The product is subjected to demulsification, filtration, washing, drying and purification to obtain a core-shell structured organosilicon toughening agent.

[0023] Furthermore, the ratio of the amount of silicon-hydrogen bond substance of the silicone oil layer: the amount of hydroxymethyl acrylamide substance: the amount of acrylate: the amount of alkenyl cyanate substance is 1:1:2.5-4:2.5-4.

[0024] Furthermore, the preparation steps of the alkenyl cyanate are as follows: 215-217 parts by mass of o-cresol and 4.30-4.34 parts by mass of p-toluenesulfonic acid are mixed, then heated to 75-85°C and stirred to mix evenly, then heated to 125-135°C, 33.7-34.1 parts by mass of 1-isopropenyl-2-(methoxymethyl)benzene are added within 55-65 minutes, then kept warm for 4.5-5.5 hours, then cooled to 80-90°C, 20wt% sodium hydroxide aqueous solution is added dropwise to neutralize the p-toluenesulfonic acid in the reaction system, then unreacted o-cresol is removed by distillation under reduced pressure, then dissolved in boiling toluene and washed three times with 70-80°C distilled water. The washed toluene layer is cooled to -18°C, then filtered, recrystallized, and vacuum dried to obtain an intermediate product; 200 parts by mass of dichloromethane and 21.3-21.4 parts by mass of cyanogen chloride are mixed, then cooled to -5°C, and a mixture obtained by mixing 74-76 parts by mass of the intermediate product, 90-92 parts by mass of triethylamine, and 200 parts by mass of butanone is added within 35-45 minutes under nitrogen protection. The reaction temperature is controlled at -5-0°C, and the reaction is kept warm for 2 hours. After the reaction is completed, the generated triethylamine salt is removed by washing with water, followed by acid washing, alkali washing, water washing, and layering to obtain an organic phase, which is then dried over anhydrous sodium sulfate and then distilled under reduced pressure to remove dichloromethane to obtain an alkenyl cyanate.

[0025] By adopting the above technical solution, the present invention has the following beneficial effects: (1) The raw material components of the anti-aging PMMA / ASA plastic alloy of the present invention include PMMA resin, ASA resin, toughening agent B, toughening agent A, compatibilizer, antioxidant, lubricant, anti-precipitation agent, light aging resistant agent, color powder, and carbon black. It not only has the high gloss and scratch resistance of PMMA and the weather resistance of ASA, but also can reduce the precipitation of small molecules, thereby reducing the mold wiping cycle in actual injection molding production; and the PMMA / ASA alloy material has high heat resistance, and the actual injection molded product does not deform at high temperature; in addition, the alloy material can prevent light from penetrating the injection molded product, preventing light diffusion. At the same time, the anti-aging PMMA / ASA plastic alloy has high impact strength and good toughness.

[0026] (2) The anti-aging PMMA / ASA plastic alloy of the present invention introduces a toughening agent B, which is ethylene-methyl acrylate-glycidyl methacrylate. As an elastomer in the PMMA / ASA plastic alloy, it can deform and tear when subjected to stress, and acts as a stress concentration point to hinder crack propagation and improve impact toughness.

[0027] (3) The anti-aging PMMA / ASA plastic alloy of the present invention is prepared by introducing a toughening agent A, wherein the toughening agent A comprises a styrene-butadiene core layer, a silicone oil layer, and an acrylate block copolymer shell layer from the inside to the outside; the acrylate block copolymer shell layer is obtained by copolymerization of acrylate, hydroxymethyl acrylamide, and alkenyl cyanate. The prepared toughening agent A has good compatibility with PMMA resin and ASA resin, and can effectively toughen the PMMA / ASA plastic alloy and improve the impact toughness of the PMMA / ASA plastic alloy.

[0028] (4) The anti-aging PMMA / ASA plastic alloy of the present invention introduces an anti-precipitation agent, benzofuranone, because the extrusion process of the polymer is usually in an oxygen-deficient state. Under the action of high temperature or shear force, a large amount of carbon free radicals (R·) rather than alkoxy free radicals (RO·) and hydroxyl free radicals (·OH) are generated in the system; benzofuranone can effectively capture carbon free radicals.

[0029] (5) The anti-aging properties of the PMMA / ASA plastic alloy of the present invention can be effectively improved by introducing a light aging resistant additive and an antioxidant additive into the anti-aging PMMA / ASA plastic alloy.

[0030] (6) The anti-aging PMMA / ASA plastic alloy of the present invention introduces carbon black, which can effectively block the light source.

[0031] (7) The anti-aging PMMA / ASA plastic alloy of the present invention is pre-mixed at 50-110°C during preparation. During the mixing process, the cyanate ester first self-polymerizes into a dimer, which is further copolymerized to form a triazine ring. In this process, the epoxy group undergoes a polyether reaction. Finally, the triazine ring reacts with the remaining epoxy group to form an oxazolidinone, thereby further achieving the effect of toughening the PMMA / ASA plastic alloy. DETAILED DESCRIPTION

[0032] In order to better understand the above technical solution, the above technical solution will be described in detail below in conjunction with specific implementation methods.

[0033] Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without making any creative work shall fall within the scope of protection of the present invention.

[0034] The following examples are only used to more clearly illustrate the technical solutions of the present invention and are not intended to limit the scope of protection of the present invention.

[0035] (Example 1) A method for preparing an anti-aging PMMA / ASA plastic alloy comprises the following steps: (1) Prepare the raw materials according to the following components and contents: PMMA resin 56%, ASA resin 19.5%, toughening agent B 4%, toughening agent A 15%, compatibilizer 3%, antioxidant 0.2%, lubricant 0.2%, anti-precipitation agent 0.2%, light aging agent 0.5%, color powder 0.8%, carbon black 0.6%; (2) The PMMA resin, ASA resin, toughening agent B, toughening agent A, compatibilizer, antioxidant, lubricant, anti-precipitation agent, light aging agent, colorant, and carbon black prepared in step (1) were premixed in a high-speed mixer for 90 seconds, and then continued to mix at 50°C for 25 minutes; (3) The premixed material in step (2) is passed through a twin-screw extruder, melt-extruded at an extrusion temperature of 180-230° C. and a screw speed of 300 rpm, and cooled and granulated to obtain an anti-aging PMMA / ASA plastic alloy.

[0036] The melt index of PMMA resin is 2g / 10min under the test conditions of 230℃ and 3.8KG, and the Vicat softening temperature is 105℃ under the test conditions of 50℃ / hr and 50N.

[0037] The melt index of ASA resin is 20g / 10min under the test conditions of 220℃ and 10KG, and the Vicat softening temperature is 100℃ under the test conditions of 50℃ / hr and 50N.

[0038] The compatibilizer is a styrene-maleic anhydride copolymer having a melt index of 3 g / 10 min at 230° C. and 2.16 kg and a heat distortion temperature of 125° C. at 1.8 MPa, wherein the maleic anhydride content is 25%.

[0039] The antioxidant is phosphite, the lubricant is silicone, the anti-precipitation agent is benzofuranone, the light aging resistance agent is 2-(2'-hydroxy-3',5'bis(a,a-dimethylbenzyl)phenyl)benzotriazole, the color powder is a mixture of red, yellow and blue primary organic dyes for piano black, and the particle size of the carbon black is 25nm.

[0040] The preparation steps of toughening agent A are as follows: A1. 208 parts by mass of styrene monomer, 162 parts by mass of liquefied compressed butadiene monomer, 1000 parts by mass of deionized water, and 10 parts by mass of an emulsifier, benzene 35, were added to a reactor. 6 parts by mass of an initiator, potassium persulfate, was added dropwise to the reactor at a rate of 10 drops / min. The reactor temperature was maintained at 65°C. Nitrogen was introduced to remove oxygen from the deionized water and the reactor. The reactor pressure was maintained at 4 MPa. The reaction was allowed to proceed for 5 h. After the reaction, the pressure was released to obtain a core layer. A2. Add 950 parts by mass of a low-hydrogen silicone oil with a hydrogen content of 0.18% to the prepared core layer, add 5 parts by mass of a platinum catalyst, control the reaction temperature to 60 ° C, and react under nitrogen for 4h to obtain a silicone oil layer; A3. 300 parts by mass of hydroxymethyl acrylamide was added to the silicone oil layer containing a silicone structure, 187.5 parts by mass of butyl acrylate, 349.63 parts by mass of alkenyl cyanate were added, 5 parts by mass of a platinum catalyst were added under nitrogen, 6 parts by mass of potassium persulfate were added dropwise at a rate of 10 drops / min, the reaction temperature was controlled to 80 ° C, and the reaction time was controlled to 6h; A4. The product is subjected to demulsification, filtration, washing, drying and purification to obtain a core-shell structured organosilicon toughening agent.

[0041] The preparation steps of the alkenyl cyanate are as follows: 215 parts by mass of o-cresol and 4.30 parts by mass of p-toluenesulfonic acid are mixed, then heated to 75°C and stirred to mix evenly, then heated to 125°C, 33.7 parts by mass of 1-isopropenyl-2-(methoxymethyl)benzene are added within 55 minutes, and then the temperature is kept to react for 4.5 hours, then the temperature is lowered to 80°C, 20wt% sodium hydroxide aqueous solution is added dropwise to neutralize the p-toluenesulfonic acid in the reaction system, and unreacted o-cresol is removed by vacuum distillation. Then, the mixture is dissolved in boiling toluene and washed three times with 70°C distilled water. The washed toluene layer is cooled to - 18 ° C, then filtered, recrystallized, and vacuum dried to obtain an intermediate product; 200 parts by mass of dichloromethane and 21.3 parts by mass of cyanogen chloride were mixed, then cooled to -5 ° C, and a mixed solution obtained by mixing 74 parts by mass of the intermediate product, 90 parts by mass of triethylamine, and 200 parts by mass of butanone was added within 35 minutes under nitrogen protection. The reaction temperature was controlled at -5 ° C, and the reaction was kept warm for 2 hours. After the reaction was completed, the generated triethylamine salt was removed by washing with water, followed by acid washing, alkali washing, water washing, and layering to obtain an organic phase, which was then dried over anhydrous sodium sulfate and then distilled under reduced pressure to remove dichloromethane to obtain alkenyl cyanate.

[0042] (Example 2) A method for preparing an anti-aging PMMA / ASA plastic alloy comprises the following steps: (1) Prepare the raw materials according to the following components and contents: PMMA resin 58.5%, ASA resin 15%, toughening agent B 5%, toughening agent A 15%, compatibilizer 3%, antioxidant 0.3%, lubricant 0.5%, anti-precipitation agent 0.4%, light aging agent 0.8%, color powder 1%, carbon black 0.5%; (2) The PMMA resin, ASA resin, toughening agent B, toughening agent A, compatibilizer, antioxidant, lubricant, anti-precipitation agent, light aging agent, color powder, and carbon black prepared in step (1) were premixed in a high-speed mixer for 90 seconds, and then continued to mix at 90°C for 30 minutes; (3) The premixed material in step (2) is passed through a twin-screw extruder, melt-extruded at an extrusion temperature of 180-230° C. and a screw speed of 250 rpm, cooled and granulated to obtain an anti-aging PMMA / ASA plastic alloy.

[0043] The melt index of PMMA resin is 5g / 10min under the test conditions of 230℃ and 3.8KG, and the Vicat softening temperature is 100℃ under the test conditions of 50℃ / hr and 50N.

[0044] The melt index of ASA resin is 15g / 10min under the test conditions of 220℃ and 10KG, and the Vicat softening temperature is 105℃ under the test conditions of 50℃ / hr and 50N.

[0045] The compatibilizer is a styrene-maleic anhydride copolymer having a melt index of 5 g / 10 min at 230° C. and 2.16 kg and a heat distortion temperature of 115° C. at 1.8 MPa, wherein the maleic anhydride content is 18%.

[0046] The antioxidant is phosphite, the lubricant is silicone, the anti-precipitation agent is benzofuranone, the light aging resistance agent is 2-(2'-hydroxy-3',5'bis(a,a-dimethylbenzyl)phenyl)benzotriazole, the color powder is a mixture of red, yellow and blue primary organic dyes for piano black, and the particle size of the carbon black is 25nm.

[0047] The preparation steps of toughening agent A are as follows: A1. 208 parts by mass of styrene monomer, 162 parts by mass of liquefied compressed butadiene monomer, 1000 parts by mass of deionized water, and 10 parts by mass of an emulsifier, benzene 35, were added to a reactor. 6 parts by mass of an initiator, potassium persulfate, was added dropwise to the reactor at a rate of 10 drops / min. The reactor temperature was maintained at 65°C. Nitrogen was introduced to remove oxygen from the deionized water and the reactor. The reactor pressure was maintained at 4 MPa. The reaction was allowed to proceed for 5 h. After the reaction, the pressure was released to obtain a core layer. A2. Add 950 parts by mass of a low-hydrogen silicone oil with a hydrogen content of 0.18% to the prepared core layer, add 5 parts by mass of a platinum catalyst, control the reaction temperature to 60 ° C, and react under nitrogen for 4h to obtain a silicone oil layer; A3. 300 parts by mass of hydroxymethyl acrylamide was added to the silicone oil layer containing a silicone structure, 187.5 parts by mass of butyl acrylate, 349.63 parts by mass of alkenyl cyanate were added, 5 parts by mass of a platinum catalyst were added under nitrogen, 6 parts by mass of potassium persulfate were added dropwise at a rate of 10 drops / min, the reaction temperature was controlled to 80 ° C, and the reaction time was controlled to 6h; A4. The product is subjected to demulsification, filtration, washing, drying and purification to obtain a core-shell structured organosilicon toughening agent.

[0048] The preparation steps of the alkenyl cyanate are as follows: 216 parts by mass of o-cresol and 4.32 parts by mass of p-toluenesulfonic acid are mixed, then heated to 80°C and stirred to mix evenly, then heated to 130°C, 33.9 parts by mass of 1-isopropenyl-2-(methoxymethyl)benzene are added within 60 minutes, then kept warm for reaction for 5 hours, then cooled to 85°C, 20wt% sodium hydroxide aqueous solution is added dropwise to neutralize the p-toluenesulfonic acid in the reaction system, then unreacted o-cresol is removed by vacuum distillation, then dissolved in boiling toluene and washed three times with 75°C distilled water, and the washed toluene layer is cooled to -18 ℃, followed by filtration, recrystallization, and vacuum drying to obtain an intermediate product; 200 parts by mass of dichloromethane and 21.35 parts by mass of cyanogen chloride were mixed, and then cooled to -5℃. Under nitrogen protection, a mixed solution obtained by mixing 75 parts by mass of the intermediate product, 91 parts by mass of triethylamine, and 200 parts by mass of butanone was added within 40 minutes. The reaction temperature was controlled at -2℃, and the reaction was kept warm for 2 hours. After the reaction was completed, the generated triethylamine salt was removed by washing with water, and then acid washing, alkali washing, water washing, and layering were performed to obtain an organic phase, which was then dried over anhydrous sodium sulfate and then distilled under reduced pressure to remove dichloromethane to obtain alkenyl cyanate.

[0049] (Example 3) A method for preparing an anti-aging PMMA / ASA plastic alloy comprises the following steps: (1) Prepare the raw materials according to the following components and contents: PMMA resin 64%, ASA resin 10%, toughening agent B 6%, toughening agent A 15%, compatibilizer 2%, antioxidant 0.5%, lubricant 0.3%, anti-precipitation agent 0.3%, light aging agent 0.7%, color powder 0.8%, carbon black 0.5%; (2) The PMMA resin, ASA resin, toughening agent B, toughening agent A, compatibilizer, antioxidant, lubricant, anti-precipitation agent, light aging agent, color powder, and carbon black prepared in step (1) were premixed in a high-speed mixer for 90 seconds, and then continued to mix at 110°C for 35 minutes; (3) The premixed material in step (2) is passed through a twin-screw extruder, melt-extruded at an extrusion temperature of 180-220° C. and a screw speed of 250 rpm, cooled and granulated to obtain an anti-aging PMMA / ASA plastic alloy.

[0050] The melt index of PMMA resin is 10g / 10min under the test conditions of 230℃ and 3.8KG, and the Vicat softening temperature is 96℃ under the test conditions of 50℃ / hr and 50N.

[0051] The melt index of ASA resin is 30g / 10min under the test conditions of 220℃ and 10KG, and the Vicat softening temperature is 95℃ under the test conditions of 50℃ / hr and 50N.

[0052] The compatibilizer is a styrene-maleic anhydride copolymer having a melt index of 3 g / 10 min at 230° C. and 2.16 kg and a heat distortion temperature of 125° C. at 1.8 MPa, wherein the maleic anhydride content is 25%.

[0053] The antioxidant additive is pentaerythritol tetrakis[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], the lubricant is silicone, the anti-precipitation additive is benzofuranone, the light aging resistance additive is 2-(2'-hydroxy-3',5'bis(a,a-dimethylbenzyl)phenyl)benzotriazole, the color powder is a mixture of red, yellow and blue primary organic dyes for piano black, and the particle size of carbon black is 25nm.

[0054] The preparation steps of toughening agent A are as follows: A1. 208 parts by mass of styrene monomer, 162 parts by mass of liquefied compressed butadiene monomer, 1000 parts by mass of deionized water, and 10 parts by mass of an emulsifier, benzene 35, were added to a reactor. 6 parts by mass of an initiator, potassium persulfate, was added dropwise to the reactor at a rate of 10 drops / min. The reactor temperature was maintained at 65°C. Nitrogen was introduced to remove oxygen from the deionized water and the reactor. The reactor pressure was maintained at 4 MPa. The reaction was allowed to proceed for 5 h. After the reaction, the pressure was released to obtain a core layer. A2. Add 950 parts by mass of a low-hydrogen silicone oil with a hydrogen content of 0.18% to the prepared core layer, add 5 parts by mass of a platinum catalyst, control the reaction temperature to 60 ° C, and react under nitrogen for 4h to obtain a silicone oil layer; A3. 300 parts by mass of hydroxymethyl acrylamide was added to the silicone oil layer containing a silicone structure, 187.5 parts by mass of butyl acrylate, 349.63 parts by mass of alkenyl cyanate were added, 5 parts by mass of a platinum catalyst were added under nitrogen, 6 parts by mass of potassium persulfate were added dropwise at a rate of 10 drops / min, the reaction temperature was controlled to 80 ° C, and the reaction time was controlled to 6h; A4. The product is subjected to demulsification, filtration, washing, drying and purification to obtain a core-shell structured organosilicon toughening agent.

[0055] The preparation steps of the alkenyl cyanate are as follows: 217 parts by mass of o-cresol and 4.34 parts by mass of p-toluenesulfonic acid are mixed, then heated to 85° C. and stirred to mix evenly, then heated to 135° C., 34.1 parts by mass of 1-isopropenyl-2-(methoxymethyl)benzene are added within 65 minutes, then kept warm for reaction for 5.5 hours, then cooled to 90° C., 20wt% sodium hydroxide aqueous solution is added dropwise to neutralize the p-toluenesulfonic acid in the reaction system, then unreacted o-cresol is removed by distillation under reduced pressure, then dissolved in boiling toluene and washed three times with 80° C. distilled water, and the washed toluene layer is cooled to - 18 ° C, then filtered, recrystallized, and vacuum dried to obtain an intermediate product; 200 parts by mass of dichloromethane and 21.4 parts by mass of cyanogen chloride were mixed, then cooled to -5 ° C, and a mixed solution obtained by mixing 76 parts by mass of the intermediate product, 92 parts by mass of triethylamine, and 200 parts by mass of butanone was added within 45 minutes under nitrogen protection. The reaction temperature was controlled at 0 ° C, and the reaction was kept warm for 2 hours. After the reaction was completed, the generated triethylamine salt was removed by washing with water, followed by acid washing, alkali washing, water washing, and layering to obtain an organic phase, which was then dried over anhydrous sodium sulfate and then distilled under reduced pressure to remove dichloromethane to obtain alkenyl cyanate.

[0056] (Example 4) A method for preparing an anti-aging PMMA / ASA plastic alloy comprises the following steps: (1) Prepare the raw materials according to the following components and contents: PMMA resin 50%, ASA resin 20%, toughening agent B 5%, toughening agent A 18%, compatibilizer 4%, antioxidant 0.5%, lubricant 0.2%, anti-precipitation agent 0.3%, light aging agent 0.8%, color powder 0.6%, carbon black 0.6%; (2) The PMMA resin, ASA resin, toughening agent B, toughening agent A, compatibilizer, antioxidant, lubricant, anti-precipitation agent, light aging agent, color powder, and carbon black prepared in step (1) were premixed in a high-speed mixer for 90 seconds, and then continued to mix at 90°C for 30 minutes; (3) The premixed material in step (2) is passed through a twin-screw extruder, melt-extruded at an extrusion temperature of 180-230° C. and a screw speed of 250 rpm, cooled and granulated to obtain an anti-aging PMMA / ASA plastic alloy.

[0057] The melt index of PMMA resin is 2g / 10min under the test conditions of 230℃ and 3.8KG, and the Vicat softening temperature is 105℃ under the test conditions of 50℃ / hr and 50N.

[0058] The melt index of ASA resin is 20g / 10min under the test conditions of 220℃ and 10KG, and the Vicat softening temperature is 100℃ under the test conditions of 50℃ / hr and 50N.

[0059] The compatibilizer is a styrene-maleic anhydride copolymer having a melt index of 3 g / 10 min at 230° C. and 2.16 kg and a heat distortion temperature of 125° C. at 1.8 MPa, wherein the maleic anhydride content is 25%.

[0060] The antioxidant additive is pentaerythritol tetrakis[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], the lubricant is polyethylene wax, the anti-precipitation additive is benzofuranone, the light aging resistance additive is a hindered amine light stabilizer, the color powder is a mixture of red, yellow and blue primary organic dyes for piano black, and the particle size of the carbon black is 30nm.

[0061] The preparation steps of toughening agent A are as follows: A1. 208 parts by mass of styrene monomer, 162 parts by mass of liquefied compressed butadiene monomer, 1000 parts by mass of deionized water, and 10 parts by mass of an emulsifier, benzene 35, were added to a reactor. 6 parts by mass of an initiator, potassium persulfate, was added dropwise to the reactor at a rate of 10 drops / min. The reactor temperature was maintained at 65°C. Nitrogen was introduced to remove oxygen from the deionized water and the reactor. The reactor pressure was maintained at 4 MPa. The reaction was allowed to proceed for 5 h. After the reaction, the pressure was released to obtain a core layer. A2. Add 950 parts by mass of a low-hydrogen silicone oil with a hydrogen content of 0.18% to the prepared core layer, add 5 parts by mass of a platinum catalyst, control the reaction temperature to 60 ° C, and react under nitrogen for 4h to obtain a silicone oil layer; A3. 300 parts by mass of hydroxymethyl acrylamide was added to the silicone oil layer containing a silicone structure, 187.5 parts by mass of butyl acrylate, 349.63 parts by mass of alkenyl cyanate were added, 5 parts by mass of a platinum catalyst were added under nitrogen, 6 parts by mass of potassium persulfate were added dropwise at a rate of 10 drops / min, the reaction temperature was controlled to 80 ° C, and the reaction time was controlled to 6h; A4. The product is subjected to demulsification, filtration, washing, drying and purification to obtain a core-shell structured organosilicon toughening agent.

[0062] The preparation steps of the alkenyl cyanate are as follows: 216 parts by mass of o-cresol and 4.32 parts by mass of p-toluenesulfonic acid are mixed, then heated to 80°C and stirred to mix evenly, then heated to 130°C, 33.9 parts by mass of 1-isopropenyl-2-(methoxymethyl)benzene are added within 60 minutes, then kept warm for reaction for 5 hours, then cooled to 85°C, 20wt% sodium hydroxide aqueous solution is added dropwise to neutralize the p-toluenesulfonic acid in the reaction system, then unreacted o-cresol is removed by vacuum distillation, then dissolved in boiling toluene and washed three times with 75°C distilled water, and the washed toluene layer is cooled to -18 ℃, followed by filtration, recrystallization, and vacuum drying to obtain an intermediate product; 200 parts by mass of dichloromethane and 21.35 parts by mass of cyanogen chloride were mixed, and then cooled to -5℃. Under nitrogen protection, a mixed solution obtained by mixing 75 parts by mass of the intermediate product, 91 parts by mass of triethylamine, and 200 parts by mass of butanone was added within 40 minutes. The reaction temperature was controlled at -2℃, and the reaction was kept warm for 2 hours. After the reaction was completed, the generated triethylamine salt was removed by washing with water, and then acid washing, alkali washing, water washing, and layering were performed to obtain an organic phase, which was then dried over anhydrous sodium sulfate and then distilled under reduced pressure to remove dichloromethane to obtain alkenyl cyanate.

[0063] (Example 5) A method for preparing an anti-aging PMMA / ASA plastic alloy comprises the following steps: (1) Prepare the raw materials according to the following components and contents: PMMA resin 56%, ASA resin 20%, toughening agent B 5%, toughening agent A 14%, compatibilizer 2%, antioxidant 0.5%, lubricant 0.5%, anti-precipitation agent 0.5%, light aging agent 1%, color powder 1%, carbon black 0.5%; (2) The PMMA resin, ASA resin, toughening agent B, toughening agent A, compatibilizer, antioxidant, lubricant, anti-precipitation agent, light aging agent, color powder, and carbon black prepared in step (1) were premixed in a high-speed mixer for 90 seconds, and then continued to mix at 90°C for 30 minutes; (3) The premixed material in step (2) is passed through a twin-screw extruder, melt-extruded at an extrusion temperature of 180-230° C. and a screw speed of 250 rpm, cooled and granulated to obtain an anti-aging PMMA / ASA plastic alloy.

[0064] PMMA Resin 1 has a melt index of 2 g / 10 min at 230°C and 3.8 kg, and a Vicat softening temperature of 105°C at 50°C / hr and 50 N. PMMA Resin 2 has a melt index of 10 g / 10 min at 230°C and 3.8 kg, and a Vicat softening temperature of 96°C at 50°C / hr and 50 N. The ratio of PMMA Resin 1 to PMMA Resin 2 is 4:1.

[0065] ASA Resin 1 had a melt index of 20 g / 10 min at 220°C and 10 kg, and a Vicat softening temperature of 100°C at 50°C / hr and 50 N. ASA Resin 2 had a melt index of 15 g / 10 min at 220°C and 10 kg, and a Vicat softening temperature of 105°C at 50°C / hr and 50 N. The ratio of ASA Resin 1 to ASA Resin 2 was 4:1. Compatibilizer 1, a styrene-maleic anhydride copolymer with a melt index of 3 g / 10 min at 230°C and 2.16 kg, and a heat deflection temperature of 125°C at 1.8 MPa, was used as the compatibilizer. The maleic anhydride content was 25%. Compatibilizer 2, a styrene-maleic anhydride copolymer with a melt index of 5 g / 10 min at 230°C and 2.16 kg and a heat deflection temperature of 115°C at 1.8 MPa, was used as the compatibilizer. The maleic anhydride content was 18%. The ratio of Compatibilizer 1 to Compatibilizer 2 was 1:1.

[0066] The antioxidant additive is pentaerythritol tetrakis[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], the lubricant is silicone, the anti-precipitation additive is benzofuranone, the light aging resistance additive is a hindered amine light stabilizer, the color powder is a mixture of red, yellow and blue primary organic dyes for piano black, and the particle size of the carbon black is 20nm.

[0067] The preparation steps of toughening agent A are as follows: A1. 208 parts by mass of styrene monomer, 162 parts by mass of liquefied compressed butadiene monomer, 1000 parts by mass of deionized water, and 10 parts by mass of an emulsifier, benzene 35, were added to a reactor. 6 parts by mass of an initiator, potassium persulfate, was added dropwise to the reactor at a rate of 10 drops / min. The reactor temperature was maintained at 65°C. Nitrogen was introduced to remove oxygen from the deionized water and the reactor. The reactor pressure was maintained at 4 MPa. The reaction was allowed to proceed for 5 h. After the reaction, the pressure was released to obtain a core layer. A2. Add 950 parts by mass of a low-hydrogen silicone oil with a hydrogen content of 0.18% to the prepared core layer, add 5 parts by mass of a platinum catalyst, control the reaction temperature to 60 ° C, and react under nitrogen for 4h to obtain a silicone oil layer; A3. 300 parts by mass of hydroxymethyl acrylamide was added to the silicone oil layer containing a silicone structure, 187.5 parts by mass of butyl acrylate, 349.63 parts by mass of alkenyl cyanate were added, 5 parts by mass of a platinum catalyst were added under nitrogen, 6 parts by mass of potassium persulfate were added dropwise at a rate of 10 drops / min, the reaction temperature was controlled to 80 ° C, and the reaction time was controlled to 6h; A4. The product is subjected to demulsification, filtration, washing, drying and purification to obtain a core-shell structured organosilicon toughening agent.

[0068] The preparation steps of the alkenyl cyanate are as follows: 216 parts by mass of o-cresol and 4.32 parts by mass of p-toluenesulfonic acid are mixed, then heated to 80°C and stirred to mix evenly, then heated to 130°C, 33.9 parts by mass of 1-isopropenyl-2-(methoxymethyl)benzene are added within 60 minutes, then kept warm for reaction for 5 hours, then cooled to 85°C, 20wt% sodium hydroxide aqueous solution is added dropwise to neutralize the p-toluenesulfonic acid in the reaction system, then unreacted o-cresol is removed by vacuum distillation, then dissolved in boiling toluene and washed three times with 75°C distilled water, and the washed toluene layer is cooled to -18 ℃, followed by filtration, recrystallization, and vacuum drying to obtain an intermediate product; 200 parts by mass of dichloromethane and 21.35 parts by mass of cyanogen chloride were mixed, and then cooled to -5℃. Under nitrogen protection, a mixed solution obtained by mixing 75 parts by mass of the intermediate product, 91 parts by mass of triethylamine, and 200 parts by mass of butanone was added within 40 minutes. The reaction temperature was controlled at -2℃, and the reaction was kept warm for 2 hours. After the reaction was completed, the generated triethylamine salt was removed by washing with water, and then acid washing, alkali washing, water washing, and layering were performed to obtain an organic phase, which was then dried over anhydrous sodium sulfate and then distilled under reduced pressure to remove dichloromethane to obtain alkenyl cyanate.

[0069] (Comparative Example 1) A method for preparing an anti-aging PMMA / ASA plastic alloy comprises the following steps: (1) Prepare the raw materials according to the following components and contents: PMMA resin 50.9%, ASA resin 20%, toughening agent B 5%, toughening agent A 18%, compatibilizer 4%, antioxidant 0.5%, lubricant 0.2%, light aging agent 0.8%, color powder 0.6%; (2) The PMMA resin, ASA resin, toughening agent B, toughening agent A, compatibilizer, antioxidant, lubricant, anti-precipitation agent, light aging agent, color powder, and carbon black prepared in step (1) were premixed in a high-speed mixer for 90 seconds, and then continued to mix at 90°C for 30 minutes; (3) The premixed material in step (2) is passed through a twin-screw extruder, melt-extruded at an extrusion temperature of 180-230° C. and a screw speed of 250 rpm, cooled and granulated to obtain an anti-aging PMMA / ASA plastic alloy.

[0070] The melt index of PMMA resin is 2g / 10min under the test conditions of 230℃ and 3.8KG, and the Vicat softening temperature is 105℃ under the test conditions of 50℃ / hr and 50N.

[0071] The melt index of ASA resin is 20g / 10min under the test conditions of 220℃ and 10KG, and the Vicat softening temperature is 100℃ under the test conditions of 50℃ / hr and 50N.

[0072] The compatibilizer is a styrene-maleic anhydride copolymer having a melt index of 3 g / 10 min at 230° C. and 2.16 kg and a heat distortion temperature of 125° C. at 1.8 MPa, wherein the maleic anhydride content is 25%.

[0073] The antioxidant is pentaerythritol tetrakis[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], the lubricant is polyethylene wax, the light aging resistance is a hindered amine light stabilizer, and the color powder is a toner prepared by mixing red, yellow and blue primary organic dyes for piano black.

[0074] The preparation steps of toughening agent A are as follows: A1. 208 parts by mass of styrene monomer, 162 parts by mass of liquefied compressed butadiene monomer, 1000 parts by mass of deionized water, and 10 parts by mass of an emulsifier, benzene 35, were added to a reactor. 6 parts by mass of an initiator, potassium persulfate, was added dropwise to the reactor at a rate of 10 drops / min. The reactor temperature was maintained at 65°C. Nitrogen was introduced to remove oxygen from the deionized water and the reactor. The reactor pressure was maintained at 4 MPa. The reaction was allowed to proceed for 5 h. After the reaction, the pressure was released to obtain a core layer. A2. Add 950 parts by mass of a low-hydrogen silicone oil with a hydrogen content of 0.18% to the prepared core layer, add 5 parts by mass of a platinum catalyst, control the reaction temperature to 60 ° C, and react under nitrogen for 4h to obtain a silicone oil layer; A3. 300 parts by mass of hydroxymethyl acrylamide was added to the silicone oil layer containing a silicone structure, 187.5 parts by mass of butyl acrylate, 349.63 parts by mass of alkenyl cyanate were added, 5 parts by mass of a platinum catalyst were added under nitrogen, 6 parts by mass of potassium persulfate were added dropwise at a rate of 10 drops / min, the reaction temperature was controlled to 80 ° C, and the reaction time was controlled to 6h; A4. The product is subjected to demulsification, filtration, washing, drying and purification to obtain a core-shell structured organosilicon toughening agent.

[0075] The preparation steps of the alkenyl cyanate are as follows: 216 parts by mass of o-cresol and 4.32 parts by mass of p-toluenesulfonic acid are mixed, then heated to 80°C and stirred to mix evenly, then heated to 130°C, 33.9 parts by mass of 1-isopropenyl-2-(methoxymethyl)benzene are added within 60 minutes, then kept warm for reaction for 5 hours, then cooled to 85°C, 20wt% sodium hydroxide aqueous solution is added dropwise to neutralize the p-toluenesulfonic acid in the reaction system, then unreacted o-cresol is removed by vacuum distillation, then dissolved in boiling toluene and washed three times with 75°C distilled water, and the washed toluene layer is cooled to -18 ℃, followed by filtration, recrystallization, and vacuum drying to obtain an intermediate product; 200 parts by mass of dichloromethane and 21.35 parts by mass of cyanogen chloride were mixed, and then cooled to -5℃. Under nitrogen protection, a mixed solution obtained by mixing 75 parts by mass of the intermediate product, 91 parts by mass of triethylamine, and 200 parts by mass of butanone was added within 40 minutes. The reaction temperature was controlled at -2℃, and the reaction was kept warm for 2 hours. After the reaction was completed, the generated triethylamine salt was removed by washing with water, and then acid washing, alkali washing, water washing, and layering were performed to obtain an organic phase, which was then dried over anhydrous sodium sulfate and then distilled under reduced pressure to remove dichloromethane to obtain alkenyl cyanate.

[0076] (Comparative Example 2) A method for preparing an anti-aging PMMA / ASA plastic alloy comprises the following steps: (1) Prepare the raw materials according to the following components and contents: PMMA resin 54.5%, ASA resin 20%, toughening agent B 5%, toughening agent A 14%, compatibilizer 2.5%, antioxidant 0.5%, lubricant 0.5%, light aging agent 1%, color powder 1%, carbon black 1%; (2) The PMMA resin, ASA resin, toughening agent B, toughening agent A, compatibilizer, antioxidant, lubricant, anti-precipitation agent, light aging agent, color powder, and carbon black prepared in step (1) were premixed in a high-speed mixer for 90 seconds, and then continued to mix at 90°C for 30 minutes; (3) The premixed material in step (2) is passed through a twin-screw extruder, melt-extruded at an extrusion temperature of 180-230° C. and a screw speed of 250 rpm, cooled and granulated to obtain an anti-aging PMMA / ASA plastic alloy.

[0077] The preparation steps of toughening agent A are as follows: A1. 208 parts by mass of styrene monomer, 162 parts by mass of liquefied compressed butadiene monomer, 1000 parts by mass of deionized water, and 10 parts by mass of an emulsifier, benzene 35, were added to a reactor. 6 parts by mass of an initiator, potassium persulfate, was added dropwise to the reactor at a rate of 10 drops / min. The reactor temperature was maintained at 65°C. Nitrogen was introduced to remove oxygen from the deionized water and the reactor. The reactor pressure was maintained at 4 MPa. The reaction was allowed to proceed for 5 h. After the reaction, the pressure was released to obtain a core layer. A2. Add 950 parts by mass of a low-hydrogen silicone oil with a hydrogen content of 0.18% to the prepared core layer, add 5 parts by mass of a platinum catalyst, control the reaction temperature to 60 ° C, and react under nitrogen for 4h to obtain a silicone oil layer; A3. 300 parts by mass of hydroxymethyl acrylamide was added to the silicone oil layer containing a silicone structure, 187.5 parts by mass of butyl acrylate, 349.63 parts by mass of alkenyl cyanate were added, 5 parts by mass of a platinum catalyst were added under nitrogen, 6 parts by mass of potassium persulfate were added dropwise at a rate of 10 drops / min, the reaction temperature was controlled to 80 ° C, and the reaction time was controlled to 6h; A4. The product is subjected to demulsification, filtration, washing, drying and purification to obtain a core-shell structured organosilicon toughening agent.

[0078] The preparation steps of the alkenyl cyanate are as follows: 216 parts by mass of o-cresol and 4.32 parts by mass of p-toluenesulfonic acid are mixed, then heated to 80°C and stirred to mix evenly, then heated to 130°C, 33.9 parts by mass of 1-isopropenyl-2-(methoxymethyl)benzene are added within 60 minutes, then kept warm for reaction for 5 hours, then cooled to 85°C, 20wt% sodium hydroxide aqueous solution is added dropwise to neutralize the p-toluenesulfonic acid in the reaction system, then unreacted o-cresol is removed by vacuum distillation, then dissolved in boiling toluene and washed three times with 75°C distilled water, and the washed toluene layer is cooled to -18 ℃, followed by filtration, recrystallization, and vacuum drying to obtain an intermediate product; 200 parts by mass of dichloromethane and 21.35 parts by mass of cyanogen chloride were mixed, and then cooled to -5℃. Under nitrogen protection, a mixed solution obtained by mixing 75 parts by mass of the intermediate product, 91 parts by mass of triethylamine, and 200 parts by mass of butanone was added within 40 minutes. The reaction temperature was controlled at -2℃, and the reaction was kept warm for 2 hours. After the reaction was completed, the generated triethylamine salt was removed by washing with water, and then acid washing, alkali washing, water washing, and layering were performed to obtain an organic phase, which was then dried over anhydrous sodium sulfate and then distilled under reduced pressure to remove dichloromethane to obtain alkenyl cyanate.

[0079] (Comparative Example 3) A method for preparing an anti-aging PMMA / ASA plastic alloy comprises the following steps: (1) Prepare the raw materials according to the following components and contents: PMMA resin 63.5%, ASA resin 15%, toughening agent A 15%, compatibilizer 3%, antioxidant 0.3%, lubricant 0.5%, anti-precipitation agent 0.4%, light aging agent 0.8%, color powder 1%, carbon black 0.5%; (2) The PMMA resin, ASA resin, toughening agent B, toughening agent A, compatibilizer, antioxidant, lubricant, anti-precipitation agent, light aging agent, color powder, and carbon black prepared in step (1) were premixed in a high-speed mixer for 90 seconds, and then continued to mix at 90°C for 30 minutes; (3) The premixed material in step (2) is passed through a twin-screw extruder, melt-extruded at an extrusion temperature of 180-230° C. and a screw speed of 250 rpm, cooled and granulated to obtain an anti-aging PMMA / ASA plastic alloy.

[0080] The melt index of PMMA resin is 5g / 10min under the test conditions of 230℃ and 3.8KG, and the Vicat softening temperature is 100℃ under the test conditions of 50℃ / hr and 50N.

[0081] The melt index of ASA resin is 15g / 10min under the test conditions of 220℃ and 10KG, and the Vicat softening temperature is 105℃ under the test conditions of 50℃ / hr and 50N.

[0082] The compatibilizer is a styrene-maleic anhydride copolymer having a melt index of 5 g / 10 min at 230° C. and 2.16 kg and a heat distortion temperature of 115° C. at 1.8 MPa, wherein the maleic anhydride content is 18%.

[0083] The antioxidant is phosphite, the lubricant is silicone, the anti-precipitation agent is benzofuranone, the light aging resistance agent is 2-(2'-hydroxy-3',5'bis(a,a-dimethylbenzyl)phenyl)benzotriazole, the color powder is a mixture of red, yellow and blue primary organic dyes for piano black, and the particle size of the carbon black is 25nm.

[0084] The preparation steps of toughening agent A are as follows: A1. 208 parts by mass of styrene monomer, 162 parts by mass of liquefied compressed butadiene monomer, 1000 parts by mass of deionized water, and 10 parts by mass of an emulsifier, benzene 35, were added to a reactor. 6 parts by mass of an initiator, potassium persulfate, was added dropwise to the reactor at a rate of 10 drops / min. The reactor temperature was maintained at 65°C. Nitrogen was introduced to remove oxygen from the deionized water and the reactor. The reactor pressure was maintained at 4 MPa. The reaction was allowed to proceed for 5 h. After the reaction, the pressure was released to obtain a core layer. A2. Add 950 parts by mass of a low-hydrogen silicone oil with a hydrogen content of 0.18% to the prepared core layer, add 5 parts by mass of a platinum catalyst, control the reaction temperature to 60 ° C, and react under nitrogen for 4h to obtain a silicone oil layer; A3. 300 parts by mass of hydroxymethyl acrylamide was added to the silicone oil layer containing a silicone structure, 187.5 parts by mass of butyl acrylate, 349.63 parts by mass of alkenyl cyanate were added, 5 parts by mass of a platinum catalyst were added under nitrogen, 6 parts by mass of potassium persulfate were added dropwise at a rate of 10 drops / min, the reaction temperature was controlled to 80 ° C, and the reaction time was controlled to 6h; A4. The product is subjected to demulsification, filtration, washing, drying and purification to obtain a core-shell structured organosilicon toughening agent.

[0085] The preparation steps of the alkenyl cyanate are as follows: 216 parts by mass of o-cresol and 4.32 parts by mass of p-toluenesulfonic acid are mixed, then heated to 80°C and stirred to mix evenly, then heated to 130°C, 33.9 parts by mass of 1-isopropenyl-2-(methoxymethyl)benzene are added within 60 minutes, then kept warm for reaction for 5 hours, then cooled to 85°C, 20wt% sodium hydroxide aqueous solution is added dropwise to neutralize the p-toluenesulfonic acid in the reaction system, then unreacted o-cresol is removed by vacuum distillation, then dissolved in boiling toluene and washed three times with 75°C distilled water, and the washed toluene layer is cooled to -18 ℃, followed by filtration, recrystallization, and vacuum drying to obtain an intermediate product; 200 parts by mass of dichloromethane and 21.35 parts by mass of cyanogen chloride were mixed, and then cooled to -5℃. Under nitrogen protection, a mixed solution obtained by mixing 75 parts by mass of the intermediate product, 91 parts by mass of triethylamine, and 200 parts by mass of butanone was added within 40 minutes. The reaction temperature was controlled at -2℃, and the reaction was kept warm for 2 hours. After the reaction was completed, the generated triethylamine salt was removed by washing with water, and then acid washing, alkali washing, water washing, and layering were performed to obtain an organic phase, which was then dried over anhydrous sodium sulfate and then distilled under reduced pressure to remove dichloromethane to obtain alkenyl cyanate.

[0086] (Comparative Example 4) A method for preparing an anti-aging PMMA / ASA plastic alloy comprises the following steps: (1) Prepare the raw materials according to the following components and contents: PMMA resin 58.5%, ASA resin 15%, toughening agent B 5%, toughening agent A 15%, compatibilizer 3%, antioxidant 0.3%, lubricant 0.5%, anti-precipitation agent 0.4%, light aging agent 0.8%, color powder 1%, carbon black 0.5%; (2) The PMMA resin, ASA resin, toughening agent B, toughening agent A, compatibilizer, antioxidant, lubricant, anti-precipitation agent, light aging agent, color powder, and carbon black prepared in step (1) were premixed in a high-speed mixer for 90 seconds, and then continued to mix at 90°C for 30 minutes; (3) The premixed material in step (2) is passed through a twin-screw extruder, melt-extruded at an extrusion temperature of 180-230° C. and a screw speed of 250 rpm, cooled and granulated to obtain an anti-aging PMMA / ASA plastic alloy.

[0087] The melt index of PMMA resin is 5g / 10min under the test conditions of 230℃ and 3.8KG, and the Vicat softening temperature is 100℃ under the test conditions of 50℃ / hr and 50N.

[0088] The melt index of ASA resin is 15g / 10min under the test conditions of 220℃ and 10KG, and the Vicat softening temperature is 105℃ under the test conditions of 50℃ / hr and 50N.

[0089] The compatibilizer is a styrene-maleic anhydride copolymer having a melt index of 5 g / 10 min at 230° C. and 2.16 kg and a heat distortion temperature of 115° C. at 1.8 MPa, wherein the maleic anhydride content is 18%.

[0090] The antioxidant is phosphite, the lubricant is silicone, the anti-precipitation agent is benzofuranone, the light aging resistance agent is 2-(2'-hydroxy-3',5'bis(a,a-dimethylbenzyl)phenyl)benzotriazole, the color powder is a mixture of red, yellow and blue primary organic dyes for piano black, and the particle size of the carbon black is 25nm.

[0091] The preparation steps of toughening agent A are as follows: A1. 208 parts by mass of styrene monomer, 162 parts by mass of liquefied compressed butadiene monomer, 1000 parts by mass of deionized water, and 10 parts by mass of an emulsifier, benzene 35, were added to a reactor. 6 parts by mass of an initiator, potassium persulfate, was added dropwise to the reactor at a rate of 10 drops / min. The reactor temperature was maintained at 65°C. Nitrogen was introduced to remove oxygen from the deionized water and the reactor. The reactor pressure was maintained at 4 MPa. The reaction was allowed to proceed for 5 h. After the reaction, the pressure was released to obtain a core layer. A2. Add 950 parts by mass of a low-hydrogen silicone oil with a hydrogen content of 0.18% to the prepared core layer, add 5 parts by mass of a platinum catalyst, control the reaction temperature to 60 ° C, and react under nitrogen for 4h to obtain a silicone oil layer; A3 was added to the silicone oil layer containing a silicone structure 300 parts by mass of hydroxymethyl acrylamide, 375 parts by mass of butyl acrylate was added, 5 parts by mass of a platinum catalyst was added under nitrogen, 6 parts by mass of potassium persulfate were added dropwise at a rate of 10 drops / min, the reaction temperature was controlled to 80 ° C, the reaction time was controlled to 6h; A4. The product is subjected to demulsification, filtration, washing, drying and purification to obtain a core-shell structured organosilicon toughening agent.

[0092] Effect Examples Table 1 below shows the performance test results of the anti-aging PMMA / ASA plastic alloys of Examples 1 to 5 and Comparative Examples 1 to 4: Table 1

[0093] As can be seen from Table 1, the atomization of Examples 1 to 5 and Comparative Examples 3 to 4 is lower than that of Comparative Examples 1 to 2, and Comparative Examples 1 to 2 are light-transmitting; the precipitation of small molecules and light transmittance of the anti-aging PMMA / ASA plastic alloys with the addition of anti-precipitation additives and carbon black are better than those of Comparative Examples 1 to 2 under the same test conditions.

[0094] As can be seen from Table 1, the impact strength of the aging-resistant PMMA / ASA plastic alloys of Examples 1-5 and Comparative Examples 1-2 is significantly higher than that of Comparative Examples 3-4; wherein Comparative Example 3 does not add toughening agent B, and Comparative Example 4 toughening agent A shell is obtained only by copolymerization of acrylate and hydroxymethyl acrylamide, and the impact toughness of the obtained aging-resistant PMMA / ASA plastic alloys is significantly better than that of Comparative Examples 3-4 under the same test conditions in Examples 1-5 and Comparative Examples 1-2; This indicates that the aging-resistant PMMA / ASA plastic alloy of the present invention is toughened simultaneously by the addition of toughening agent B and the toughening agent A shell obtained by copolymerization of acrylate, hydroxymethyl acrylamide and alkenyl cyanate, which can act synergistically, thereby further improving the impact toughness of the aging-resistant PMMA / ASA plastic alloy.

[0095] The specific embodiments described above further illustrate the objectives, technical solutions and beneficial effects of the present invention in detail. It should be understood that the above are only specific embodiments of the present invention and are not intended to limit the present invention. Any modifications, equivalent substitutions, improvements, etc. made within the spirit and principles of the present invention should be included in the scope of protection of the present invention.

Claims

1. An anti-aging PMMA / ASA plastic alloy, characterized in that: The raw material components include, by mass, 50-70% PMMA resin, 10-20% ASA resin, 4-6% toughening agent B, 10-20% toughening agent A, 2-5% compatibilizer, 0.2-0.5% antioxidant, 0.1-0.5% lubricant, 0.2-0.5% anti-precipitation agent, 0.5-1% light aging agent, 0.5-1% color powder, and 0.5-1% carbon black.

2. The anti-aging PMMA / ASA plastic alloy according to claim 1, wherein The toughening agent A comprises, from the inside to the outside, a styrene-butadiene core layer, a silicone oil layer, and an acrylate block copolymer shell layer.

3. The anti-aging PMMA / ASA plastic alloy according to claim 2, wherein The acrylic ester block copolymer shell layer is obtained by copolymerizing acrylic ester, hydroxymethyl acrylamide and alkenyl cyanate.

4. The anti-aging PMMA / ASA plastic alloy according to claim 1, wherein The toughening agent B is ethylene-methyl acrylate-glycidyl methacrylate.

5. The preparation method of the anti-aging PMMA / ASA polyblend according to any one of claims 1 to 4, wherein The method comprises the following preparation steps: (1) Prepare the raw materials according to the following components and contents: PMMA resin 50~70%, ASA resin 10~20%, toughening agent B4~6%, toughening agent A10~20%, compatibilizer 2%~5%, antioxidant 0.2~0.5%, lubricant 0.1~0.5%, anti-precipitation agent 0.2~0.5%, light aging agent 0.5~1%, color powder 0.5~1%, carbon black 0.5~1%; (2) The PMMA resin, ASA resin, toughening agent B, toughening agent A, compatibilizer, antioxidant, lubricant, anti-precipitation agent, light aging agent, color powder, and carbon black prepared in step (1) were premixed in a high-speed mixer for 90 seconds, and then continued to mix at 50-110°C for 25-35 minutes; (3) The premixed material in step (2) is passed through a twin-screw extruder, melt-extruded at an extrusion temperature of 180-230° C. and a screw speed of 250 rpm, cooled and granulated to obtain an anti-aging PMMA / ASA plastic alloy.

6. The preparation method of the anti-aging PMMA / ASA polystyrene according to claim 5, wherein The preparation steps of toughening agent A are as follows: A1. Styrene monomer, liquefied compressed butadiene monomer, deionized water, a water-soluble initiator, and an emulsifier are subjected to emulsion polymerization at a certain reaction temperature and under nitrogen for a period of time to obtain a non-polar core layer in a core-shell structure; A2. Add a certain amount of hydrogenated silicone oil to the prepared core layer. Under the action of a transition metal catalyst, the reaction is controlled at a certain temperature to cause addition of unsaturated double bonds in the core layer structure according to the coordination addition mechanism. The addition reaction time is controlled within a certain period of time to produce a silicone oil layer containing an organic silicon structure. A3. Acrylate, hydroxymethyl acrylamide, and alkenyl cyanate are added to the silicone oil layer containing an organosilicon structure. Unreacted hydrogen in the hydrogen-containing silicone oil dehydrogenates the hydroxyl groups in the hydroxymethyl acrylamide under the action of a transition metal catalyst; the acrylate monomer and alkenyl cyanate are subjected to an emulsion polymerization reaction to obtain a shell layer having polar groups. A4. The product is subjected to demulsification, filtration, washing, drying and purification to obtain a core-shell structured organosilicon toughening agent.

7. The preparation method of the anti-aging PMMA / ASA polystyrene according to claim 6, wherein The ratio of the amount of silicon-hydrogen bond in the silicone oil layer: the amount of hydroxymethyl acrylamide: acrylate: alkenyl cyanate is 1:1:2.5-4:2.5-4.

8. The preparation method of the anti-aging PMMA / ASA polystyrene according to claim 6, wherein The preparation steps of the alkenyl cyanate are as follows: 215-217 parts by mass of o-cresol and 4.30-4.34 parts by mass of p-toluenesulfonic acid are mixed, then heated to 75-85° C. and stirred to mix evenly, then heated to 125-135° C., 33.7-34.1 parts by mass of 1-isopropenyl-2-(methoxymethyl)benzene are added within 55-65 minutes, then kept warm for reaction for 4.5-5.5 hours, then cooled to 80-90° C., 20wt% sodium hydroxide aqueous solution is added dropwise to neutralize the p-toluenesulfonic acid in the reaction system, then unreacted o-cresol is removed by vacuum distillation, then dissolved in boiling toluene and washed three times with 70-80° C. distilled water, the washed toluene layer is cooled to -18° C., then filtered, recrystallized, and vacuum dried to obtain an intermediate product; 200 parts by mass of dichloromethane and 21.3-21.4 parts by mass of cyanogen chloride are mixed, and then cooled to -5°C. Under nitrogen protection, a mixed solution obtained by mixing 74-76 parts by mass of the intermediate product, 90-92 parts by mass of triethylamine, and 200 parts by mass of butanone is added within 35-45 minutes. The reaction temperature is controlled at -5-0°C, and the reaction is kept warm for 2 hours. After the reaction is completed, the generated triethylamine salt is removed by washing with water, and then the organic phase is acid washed, alkali washed, and washed with water. The organic phase is separated and then dried over anhydrous sodium sulfate and distilled under reduced pressure to remove dichloromethane to obtain alkenyl cyanate.

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