Anti-aging foamed highlight engineering plastic and preparation process thereof

Abstract

The invention relates to the field of high polymer materials, and discloses an anti-aging foamed highlight engineering plastic and a preparation process thereof, the foamed highlight engineering plastic comprises ABS resin, microcapsule foaming master batch, a nucleating agent, a lubricant and an antioxidant; the microcapsule foaming master batch is prepared by mixing ABS (Acrylonitrile Butadiene Styrene) resin and functional thermal expansion microspheres; the functional thermal expansion microspheres are prepared by the following steps: modifying thermal expansion microspheres by using hydroxylamine, carrying out chemical silver plating, modifying by using mercaptopropyltrimethoxysilane to obtain silver-coated thermal expansion microspheres, and condensing hydroxyl silicone oil and mercaptopropyltrimethoxysilane. The thermal expansion microspheres are prepared by introducing 2-(2-hydroxy-5-benzyl) benzotriazole by a suspension polymerization method to react with acryloyl chloride to prepare a vinyl light-stable monomer, and the functional thermal expansion microspheres are added into a matrix to prepare the vinyl light-stable monomer which is high in tensile strength, good in impact resistance, good in thermal expansion performance and good in thermal expansion performance. Meanwhile, the foaming material has good ultraviolet aging resistance, heat resistance and water resistance.

Description

Technical Field

[0001] This invention belongs to the field of polymer materials technology, specifically relating to an aging-resistant foamed high-gloss engineering plastic and its preparation process. Background Technology

[0002] Acrylonitrile-butadiene-styrene copolymer (ABS resin) is one of the five major synthetic resins. It has excellent low-temperature resistance and insulation properties; it is easy to process, has stable product dimensions, and good surface gloss; it is also easy to paint and color. It can undergo secondary processing such as surface metal spraying, electroplating, welding, hot pressing, and bonding. It is widely used in industrial fields such as machinery, automobiles, electronics, instruments, textiles, and construction. It is a thermoplastic engineering plastic with extremely wide applications.

[0003] With the development of science and technology, polymer foam materials have been rapidly developed due to their lightweight, good compressibility, and good cushioning properties. However, the performance of existing foam materials will decay under ultraviolet radiation, resulting in a significant decrease in mechanical properties and aging resistance. Although adding light stabilizers to the formulation can delay aging to some extent, these small molecule additives are prone to migration and loss, making it difficult to provide a long-lasting and stable protective effect. At the same time, existing foam materials have disadvantages such as poor heat resistance, poor mechanical properties, and poor hydrophobicity, which seriously limit their widespread application. Summary of the Invention

[0004] To address the shortcomings mentioned in the background art, the present invention aims to provide an aging-resistant foamed high-gloss engineering plastic and its preparation process. The prepared functionalized thermal expansion microspheres are added to the polymer matrix as a physical foaming agent to prepare a foamed material with high tensile strength, good impact resistance, and good UV aging resistance, heat resistance, and water resistance.

[0005] The objective of this invention can be achieved through the following technical solutions:

[0006] An aging-resistant foamed high-gloss engineering plastic comprises the following components by weight: 100 parts ABS resin, 10-25 parts microcapsule foaming masterbatch, 0.5-2 parts nucleating agent, 0.1-1 parts lubricant, and 0.1-0.6 parts antioxidant;

[0007] The preparation method of the microcapsule foaming masterbatch is as follows: ABS resin and functionalized thermal expansion microspheres are mixed evenly at a mass ratio of 9:1, and then further mixed evenly on a two-roll mill, wherein the front roll temperature and the rear roll temperature are 80℃ and 85℃ respectively, and then crushed into granules in a high-speed crusher.

[0008] The functionalized thermal expansion microspheres are prepared by using hydroxylamine to modify thermal expansion microspheres to introduce active sites on the surface of thermal expansion microspheres and then chemically plating silver to obtain silver-coated thermal expansion microspheres. Subsequently, mercaptopropyltrimethoxysilane is used to modify the silver-coated thermal expansion microspheres, and then the prepared silane-modified silver-coated thermal expansion microspheres are reacted with hydroxyl silicone oil to form the microspheres.

[0009] The thermally expandable microspheres are prepared by suspension polymerization using isopentane as a foaming agent, acrylonitrile, methyl methacrylate, butyl methacrylate, vinyl light-stabilizing monomer, hydroxyethyl methacrylate as comonomers, and magnesium hydroxide as a dispersant; the vinyl light-stabilizing monomer is prepared by esterification reaction of 2-(2-hydroxy-5-benzyl)benzotriazole with acryloyl chloride.

[0010] Preferably, the nucleating agent is one or a combination of several of organomontmorillonite, nano-calcium carbonate, silica, and nano-talc; the lubricant is one or a combination of several of pentaerythritol stearate, N,N'-ethylene bis-stearamide, and glyceryl monooleate; and the antioxidant is one or a combination of two of antioxidant 1076 and antioxidant 168.

[0011] Preferably, the preparation method of the functionalized thermally expandable microspheres includes the following steps:

[0012] A. Prepare an aqueous solution of hydroxylamine with a concentration of 1~1.5mol / L, then add thermally expanded microspheres, and stir the mixture at 65~70℃ for 10~15min. After the reaction is complete, wash and filter to obtain hydroxylamine-modified thermally expanded microspheres.

[0013] B. Take silver nitrate in deionized water, mix well, and then add ammonia dropwise until a clear and transparent solution is obtained. Then, adjust the pH of the solution to 12-12.5 using sodium hydroxide solution, and continue to slowly add ammonia dropwise until the solution is clear and transparent to obtain silver ammonia solution.

[0014] C. Add hydroxylamine-modified thermally expandable microspheres to freshly prepared silver ammonia solution and stir at room temperature for 3 hours. Then add glucose aqueous solution dropwise, controlling the dropwise addition rate to 0.5~1 drop / s. After the addition is complete, continue the reaction for 2 hours. After the reaction is complete, wash, filter and dry to obtain silver-coated thermally expandable microspheres.

[0015] D. Disperse the silver-coated thermal expansion microspheres in anhydrous ethanol, then add mercaptopropyltrimethoxysilane, and stir the reaction under a nitrogen atmosphere for 6-8 hours. After the reaction is completed, wash with anhydrous ethanol, filter and dry to obtain silane-modified silver-coated thermal expansion microspheres.

[0016] E. Disperse silane-modified silver-coated thermal expansion microspheres in isopropanol, heat to 50°C under nitrogen atmosphere, then add hydroxyl silicone oil and stannous isooctanoate and react for 2-4 hours. After the reaction is complete, filter to remove the solvent, wash the unreacted material with petroleum ether and ethylene glycol and vacuum dry to obtain functionalized thermal expansion microspheres.

[0017] Preferably, the addition ratio of silver nitrate, deionized water, hydroxylamine-modified thermal expansion microspheres and glucose aqueous solution is 0.4g:30mL:0.1g:20mL; and the concentration of glucose aqueous solution is 0.12~0.13g / mL.

[0018] Preferably, the viscosity of the hydroxyl silicone oil is 3000 cs; the mass ratio of the silane-modified silver-coated thermal expansion microspheres, the hydroxyl silicone oil, and the stannous isooctanoate is 4~7:10~12:0.1~0.15.

[0019] Preferably, the method for preparing the thermally expandable microspheres includes the following steps:

[0020] (1) Take magnesium hydroxide, polyvinylpyrrolidone, sodium nitrite and sodium chloride and add them to deionized water in sequence, stir to dissolve, and then stir at 1000 r / min for 5 min to obtain the aqueous phase;

[0021] (2) Take isopentane, acrylonitrile, methyl methacrylate, butyl methacrylate, vinyl light-stabilized monomer, hydroxyethyl methacrylate, benzoyl peroxide, and dipropylene phthalate and mix them thoroughly to obtain the oil phase of suspension polymerization;

[0022] (3) The oil phase is slowly added dropwise to the aqueous phase, and the stirring speed is maintained at 1000 r / min for 5 min to obtain an oil-in-water suspension;

[0023] (4) Pour the suspension dispersion into the reactor, purge with nitrogen three times to remove oxygen, pressurize to 0.48~0.5MPa under nitrogen atmosphere and seal, set the polymerization stirring speed to 400r / min, and react at a constant temperature of 70℃ for 20h. After the reaction is completed, cool to room temperature, depressurize and discharge the material, filter, wash and dry to obtain thermally expanded microspheres.

[0024] Preferably, in step (1), the mass ratio of magnesium hydroxide, polyvinylpyrrolidone, sodium nitrite and sodium chloride is 7.2~7.8:0.25~0.3:0.06~0.075:30.

[0025] Preferably, the preparation method of the vinyl light-stabilized monomer in step (2) includes the following steps: 2-(2-hydroxy-5-benzyl)benzotriazole, methylhydroquinone and triethylamine are placed in a reactor, tetrahydrofuran solvent is added, the mixture is heated to 55~65℃ and stirred until homogeneous, then a mixed solution of acryloyl chloride and tetrahydrofuran is added dropwise, and stirring is continued for 9~10h after the addition is completed. After the reaction is completed, the tetrahydrofuran layer is removed with a separatory funnel, deionized water is added and stirred, then filtered, the solvent is removed by rotary evaporation and recrystallized with ethanol to obtain the vinyl light-stabilized monomer.

[0026] Preferably, in step (2), the mass ratio of isopentane, acrylonitrile, methyl methacrylate, butyl methacrylate, vinyl light-stabilized monomer, hydroxyethyl methacrylate, benzoyl peroxide, and diallyl phthalate is 3:2:5:1:1~2:1:0.05:0.03.

[0027] The preparation process of the aging-resistant foamed high-gloss engineering plastic as described above includes the following steps:

[0028] S1. Weigh each component according to the weight parts, mix ABS resin, nucleating agent, lubricant and antioxidant, and then extrude and granulate. The extrusion temperature is 180~200℃ to obtain the mixture.

[0029] S2. After mixing the mixture with the microcapsule foaming masterbatch, the mixture is injected into the molded material using an injection molding machine at a temperature of 190~210℃ to obtain an aging-resistant foamed high-gloss engineering plastic.

[0030] The beneficial effects of this invention are:

[0031] This invention utilizes the esterification reaction of 2-(2-hydroxy-5-benzyl)benzotriazole with acryloyl chloride to prepare a vinyl light-stabilized monomer with benzotriazole UV-resistant groups and double bonds. Then, using suspension polymerization with low-boiling-point isopentane as a foaming agent, acrylonitrile, methyl methacrylate, butyl methacrylate, the vinyl light-stabilized monomer, and hydroxyethyl methacrylate as comonomers, and magnesium hydroxide as a dispersant, thermally expandable microspheres with UV aging resistance are prepared. Hydroxylamine is then used to modify the thermally expandable microspheres to introduce active sites on their surface, followed by chemical silver plating. Subsequently, silver-coated thermally expandable microspheres are prepared by modification with mercaptopropyltrimethoxysilane. Finally, the hydroxyl groups at both ends of hydroxyl silicone oil are condensed with mercaptopropyltrimethoxysilane to graft onto the silver-coated microspheres. The silver coating on the surface of the thermally expandable microspheres improves the compatibility between the silver-coated microspheres and the matrix. The presence of the silver layer on the surface of the thermally expandable microspheres effectively distributes the impact energy over a larger area, reducing local stress concentration at the impact point. The polysiloxane, with Si-O-Si as the main chain, has low surface free energy and excellent heat resistance. After the polysiloxane polymerizes and forms long chains on the surface of the silver-coated thermally expandable microspheres and becomes entangled, it exhibits high hydrophobicity, reducing the number of pores that could absorb water and thus significantly reducing the water absorption rate of the material. Furthermore, the polysiloxane grafted onto the surface of the silver-coated thermally expandable microspheres through chemical bonding acts as a stress concentration point under external impact, generating deformation cavitation, which improves stress transmission and dispersion capabilities, thereby greatly enhancing the impact resistance of the material. This invention prepares functionalized thermally expandable microspheres coated with silver nanoparticles and polysiloxane by modifying the surface of thermally expandable microspheres, and adds them as physical foaming agents to the polymer matrix to prepare a foamed material with high tensile strength, good impact resistance, and good UV aging resistance, heat resistance and water resistance. Detailed Implementation

[0032] The technical solutions of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative effort are within the scope of protection of the present invention.

[0033] Example 1: A method for preparing a vinyl light-stabilized monomer includes the following steps:

[0034] 32.6 g of 2-(2-hydroxy-5-benzyl)benzotriazole, 0.1 g of methylhydroquinone, and 29.3 g of triethylamine were placed in a reactor, and 200 mL of tetrahydrofuran solvent was added. The mixture was heated to 60 °C and stirred until homogeneous. Then, a mixed solution of 26.2 g of acryloyl chloride and 20 mL of tetrahydrofuran was added dropwise. After the addition was complete, the mixture was stirred for 10 h. After the reaction was completed, the tetrahydrofuran layer was removed using a separatory funnel. Deionized water was added, stirred, and filtered. The solvent was removed by rotary evaporation and the mixture was recrystallized from ethanol to obtain the vinyl light-stable monomer.

[0035] Example 2: A method for preparing thermally expandable microspheres includes the following steps:

[0036] (1) Take 45g magnesium hydroxide, 1.8g polyvinylpyrrolidone K17, 0.4g sodium nitrite and 180g sodium chloride and add them to 600mL of deionized water in sequence. Stir and dissolve thoroughly, and then stir at 1000r / min for 5min to obtain the aqueous phase.

[0037] (2) Take 36g isopentane, 24g acrylonitrile, 60g methyl methacrylate, 12g butyl methacrylate, 12g vinyl light-stabilized monomer prepared in Example 1, 12g hydroxyethyl methacrylate, 0.6g benzoyl peroxide, and 0.36g dipropylene phthalate and mix them thoroughly to obtain the oil phase of suspension polymerization.

[0038] (3) The oil phase is slowly added dropwise to the aqueous phase, and the stirring speed is maintained at 1000 r / min for 5 min to obtain an oil-in-water suspension;

[0039] (4) Pour the suspension dispersion into the reactor, purge nitrogen three times to remove oxygen, pressurize to 0.5 MPa under nitrogen atmosphere and seal, set the polymerization stirring speed to 400 r / min, and react at a constant temperature of 70℃ for 20 h. After the reaction is completed, cool to room temperature, depressurize and discharge the material. After filtration, washing and drying, thermally expanded microspheres are obtained.

[0040] Example 3: A method for preparing functionalized thermally expandable microspheres includes the following steps:

[0041] A. Prepare 50 mL of hydroxylamine aqueous solution with a concentration of 1 mol / L, then add 0.1 g of the thermally expanded microspheres prepared in Example 2, and stir at 70 °C for 10 min. After the reaction is completed, wash and filter to obtain hydroxylamine modified thermally expanded microspheres.

[0042] B. Take 0.4g of silver nitrate in 30mL of deionized water, mix well, and then add 37wt% ammonia water dropwise until a clear and transparent solution is obtained. Then adjust the pH of the solution to 12 using 50g / L sodium hydroxide solution, and continue to slowly add 37wt% ammonia water dropwise until the solution is clear and transparent to obtain silver ammonia solution.

[0043] C. Add 0.1g of hydroxylamine-modified thermal expansion microspheres to freshly prepared silver ammonia solution and stir at room temperature for 3h. Then add 20mL of 0.13g / mL glucose aqueous solution at a rate of 1 drop / s. After the addition is complete, continue the reaction for 2h. After the reaction is complete, wash, filter and dry to obtain silver-coated thermal expansion microspheres.

[0044] D. Take 0.1g of silver-coated thermal expansion microspheres and disperse them in 50mL of anhydrous ethanol. Then add 0.05mL of mercaptopropyltrimethoxysilane and stir the reaction under a nitrogen atmosphere for 8h. After the reaction is completed, wash with anhydrous ethanol, filter and dry to obtain silane-modified silver-coated thermal expansion microspheres.

[0045] E. Disperse 0.1g of silane-modified silver-coated thermal expansion microspheres in 100mL of isopropanol, heat to 50℃ under nitrogen atmosphere, then add 0.2g of hydroxyl silicone oil with a viscosity of 3000cs and 0.002g of stannous isooctanoate and react for 3h. After the reaction is complete, filter to remove the solvent, wash the unreacted material with petroleum ether and ethylene glycol and vacuum dry to obtain functionalized thermal expansion microspheres.

[0046] Example 4: A method for preparing a microcapsule foaming masterbatch is as follows: ABS resin and the functionalized thermally expandable microspheres prepared in Example 3 are mixed evenly at a mass ratio of 9:1, and then further mixed evenly on a two-roll mill, wherein the front roll temperature and the rear roll temperature are 80°C and 85°C, respectively, and then crushed into granules in a high-speed crusher.

[0047] Example 5 An aging-resistant foamed high-gloss engineering plastic, comprising the following components by weight: 100 parts ABS resin, 12 parts microcapsule foaming masterbatch prepared in Example 4, 0.6 parts organomontmorillonite nucleating agent, 0.2 parts pentaerythritol stearate lubricant, and 0.2 parts antioxidant 1076.

[0048] The preparation process of the above-mentioned aging-resistant foamed high-gloss engineering plastic includes the following steps:

[0049] S1. Weigh each component according to the weight parts, mix ABS resin, nucleating agent, lubricant and antioxidant, and then extrude and granulate. The extrusion temperature is 180~200℃ to obtain the mixture.

[0050] S2. After mixing the mixture with the microcapsule foaming masterbatch, the mixture is injected into the molded material using an injection molding machine at a temperature of 190~210℃ to obtain an aging-resistant foamed high-gloss engineering plastic.

[0051] Example 6 An aging-resistant foamed high-gloss engineering plastic, comprising the following components by weight: 100 parts ABS resin, 18 parts microcapsule foaming masterbatch prepared in Example 4, 1.2 parts organomontmorillonite nucleating agent, 0.4 parts pentaerythritol stearate lubricant, and 0.3 parts antioxidant 1076.

[0052] The preparation process of the above-mentioned aging-resistant foamed high-gloss engineering plastic is the same as that in Example 5.

[0053] Example 7 An aging-resistant foamed high-gloss engineering plastic, comprising the following components by weight: 100 parts ABS resin, 22 parts microcapsule foaming masterbatch prepared in Example 4, 1.7 parts organomontmorillonite nucleating agent, 0.8 parts pentaerythritol stearate lubricant, and 0.5 parts antioxidant 1076.

[0054] The preparation process of the above-mentioned aging-resistant foamed high-gloss engineering plastic is the same as that in Example 5.

[0055] Comparative Example 1: A method for preparing thermally expandable microspheres includes the following steps:

[0056] (1) Take 45g magnesium hydroxide, 1.8g polyvinylpyrrolidone K17, 0.4g sodium nitrite and 180g sodium chloride and add them to 600mL of deionized water in sequence. Stir and dissolve thoroughly, and then stir at 1000r / min for 5min to obtain the aqueous phase.

[0057] (2) Take 36g isopentane, 24g acrylonitrile, 60g methyl methacrylate, 24g butyl methacrylate, 12g hydroxyethyl methacrylate, 0.6g benzoyl peroxide, and 0.36g diallyl phthalate and mix them thoroughly to obtain the oil phase of suspension polymerization;

[0058] (3) The oil phase is slowly added dropwise to the aqueous phase, and the stirring speed is maintained at 1000 r / min for 5 min to obtain an oil-in-water suspension;

[0059] (4) Pour the suspension dispersion into the reactor, purge nitrogen three times to remove oxygen, pressurize to 0.5 MPa under nitrogen atmosphere and seal, set the polymerization stirring speed to 400 r / min, and react at a constant temperature of 70℃ for 20 h. After the reaction is completed, cool to room temperature, depressurize and discharge the material. After filtration, washing and drying, thermally expanded microspheres are obtained.

[0060] Comparative Example 2: A method for preparing a microcapsule foaming masterbatch is as follows: ABS resin and functionalized thermally expandable microspheres are mixed evenly at a mass ratio of 9:1, and then further mixed evenly on a two-roll mill, wherein the front roll temperature and the rear roll temperature are 80℃ and 85℃, respectively, and then crushed into granules in a high-speed crusher.

[0061] The preparation method of functionalized thermally expandable microspheres includes the following steps:

[0062] A. Prepare 50 mL of hydroxylamine aqueous solution with a concentration of 1 mol / L, then add 0.1 g of the thermally expanded microspheres prepared in Comparative Example 1, and stir at 70 °C for 10 min. After the reaction is completed, wash and filter to obtain hydroxylamine-modified thermally expanded microspheres.

[0063] B. Take 0.4g of silver nitrate in 30mL of deionized water, mix well, and then add 37wt% ammonia water dropwise until a clear and transparent solution is obtained. Then adjust the pH of the solution to 12 using 50g / L sodium hydroxide solution, and continue to slowly add 37wt% ammonia water dropwise until the solution is clear and transparent to obtain silver ammonia solution.

[0064] C. Add 0.1g of hydroxylamine-modified thermal expansion microspheres to freshly prepared silver ammonia solution and stir at room temperature for 3h. Then add 20mL of 0.13g / mL glucose aqueous solution at a rate of 1 drop / s. After the addition is complete, continue the reaction for 2h. After the reaction is complete, wash, filter and dry to obtain silver-coated thermal expansion microspheres.

[0065] D. Take 0.1g of silver-coated thermal expansion microspheres and disperse them in 50mL of anhydrous ethanol. Then add 0.05mL of mercaptopropyltrimethoxysilane and stir the reaction under a nitrogen atmosphere for 8h. After the reaction is completed, wash with anhydrous ethanol, filter and dry to obtain silane-modified silver-coated thermal expansion microspheres.

[0066] E. Disperse 0.1g of silane-modified silver-coated thermal expansion microspheres in 100mL of isopropanol, heat to 50℃ under nitrogen atmosphere, then add 0.2g of hydroxyl silicone oil with a viscosity of 3000cs and 0.002g of stannous isooctanoate and react for 3h. After the reaction is complete, filter to remove the solvent, wash the unreacted material with petroleum ether and ethylene glycol and vacuum dry to obtain functionalized thermal expansion microspheres.

[0067] Comparative Example 3: A method for preparing a microcapsule foaming masterbatch is as follows: ABS resin and functionalized thermally expandable microspheres are mixed evenly at a mass ratio of 9:1, and then further mixed evenly on a two-roll mill, wherein the front roll temperature and the rear roll temperature are 80℃ and 85℃, respectively, and then crushed into granules in a high-speed crusher.

[0068] The preparation method of functionalized thermally expandable microspheres includes the following steps:

[0069] A. Prepare 50 mL of hydroxylamine aqueous solution with a concentration of 1 mol / L, then add 0.1 g of the thermally expanded microspheres prepared in Example 2, and stir at 70 °C for 10 min. After the reaction is completed, wash and filter to obtain hydroxylamine modified thermally expanded microspheres.

[0070] B. Take 0.4g of silver nitrate in 30mL of deionized water, mix well, and then add 37wt% ammonia water dropwise until a clear and transparent solution is obtained. Then adjust the pH of the solution to 12 using 50g / L sodium hydroxide solution, and continue to slowly add 37wt% ammonia water dropwise until the solution is clear and transparent to obtain silver ammonia solution.

[0071] C. Add 0.1g of hydroxylamine-modified thermal expansion microspheres to freshly prepared silver ammonia solution and stir at room temperature for 3h. Then, add 20mL of 0.13g / mL glucose aqueous solution at a rate of 1 drop / s. After the addition is complete, continue the reaction for 2h. After the reaction is complete, wash, filter and dry to obtain functionalized thermal expansion microspheres.

[0072] Comparative Example 4: A method for preparing a microcapsule foaming masterbatch is as follows: ABS resin and the thermally expanded microspheres prepared in Example 2 are mixed evenly at a mass ratio of 9:1, and then further mixed evenly on a two-roll mill, wherein the front roll temperature and the rear roll temperature are 80°C and 85°C, respectively, and then crushed into granules in a high-speed crusher.

[0073] Comparative Example 5: An aging-resistant foamed high-gloss engineering plastic, comprising the following components by weight: 100 parts ABS resin, 22 parts microcapsule foaming masterbatch prepared in Comparative Example 2, 1.7 parts organomontmorillonite nucleating agent, 0.8 parts pentaerythritol stearate lubricant, and 0.5 parts antioxidant 1076.

[0074] The preparation process of the above-mentioned aging-resistant foamed high-gloss engineering plastic is the same as that in Example 5.

[0075] Comparative Example 6: An aging-resistant foamed high-gloss engineering plastic, comprising the following components by weight: 100 parts ABS resin, 22 parts microcapsule foaming masterbatch prepared in Comparative Example 3, 1.7 parts organomontmorillonite nucleating agent, 0.8 parts pentaerythritol stearate lubricant, and 0.5 parts antioxidant 1076.

[0076] The preparation process of the above-mentioned aging-resistant foamed high-gloss engineering plastic is the same as that in Example 5.

[0077] Comparative Example 7: An aging-resistant foamed high-gloss engineering plastic, comprising the following components by weight: 100 parts ABS resin, 22 parts microcapsule foaming masterbatch prepared in Comparative Example 4, 1.7 parts organomontmorillonite nucleating agent, 0.8 parts pentaerythritol stearate lubricant, and 0.5 parts antioxidant 1076.

[0078] The preparation process of the above-mentioned aging-resistant foamed high-gloss engineering plastic is the same as that in Example 5.

[0079] Performance testing

[0080] The performance of the foamed high-gloss engineering plastics prepared in Examples 5-7 and Comparative Examples 5-7 was tested:

[0081] (1) Mechanical property test: The tensile properties of the samples were tested according to GB / T 1040.3-2006 standard using a universal tensile testing machine. Each sample was measured 5 times and the average value was taken. The notched impact strength of the cantilever beam was tested according to GB / T 1843-2008 standard. The data results are shown in Table 1.

[0082] (2) UV aging resistance test: A 20W UV lamp was used as the light source, emitting short-wave UV light with a characteristic wavelength of 253.7nm. The UV irradiance at 20cm vertically from the center of the lamp was 1400μw / cm. 2 The sample was placed parallel to the light source in a fixed position and aged under ultraviolet light for 800 hours. The change rate of tensile strength was tested, and the data results are shown in Table 1.

[0083] (3) Water absorption rate test: The water absorption rate of the sample was tested according to ASTM D570-98 standard. The sample was cut into round slices with a diameter of 50 mm, dried in an oven at 50 ℃ for 24 h, and then cooled to room temperature. The mass was M0, accurate to 0.001 g. The weighed sample was soaked in distilled water at 23 ℃ for 24 h. The sample was removed, the surface moisture was wiped off, and the mass of the sample was weighed again, M1, accurate to 0.001 g. The formula for calculating the water absorption rate M is: M=(M1-M0) / M0×100%. The data results are shown in Table 1.

[0084] (4) Thermal stability test: The thermal stability of the sample was tested using a synchronous thermal analyzer. Approximately 5 mg of sample was weighed and placed in a crucible. The temperature was increased from room temperature to 700 °C under a nitrogen atmosphere at a rate of 10 °C / min. The data results are shown in Table 1.

[0085] Table 1 Sample performance test results

[0086]

[0087] As can be seen from the data in Table 1, the samples prepared in Examples 5-7 of this invention have high tensile strength, good impact resistance, and also possess good UV aging resistance, heat resistance, and water resistance. In Comparative Example 5, the microcapsule foaming masterbatch replaced the vinyl light-stabilizing monomer with butyl methacrylate in equal amounts during the preparation of the thermally expanded microspheres. The measured change rate of its tensile strength was significantly different compared to Examples 5-7. This is because the vinyl light-stabilizing monomer with benzotriazole UV-resistant groups through chemical bonding is beneficial to improving the long-term UV aging resistance of the sample. In Comparative Example 6, the microcapsule foaming masterbatch did not introduce polysiloxane coating during the preparation of functionalized thermally expanded microspheres. In Comparative Example 7, the microcapsule foaming masterbatch did not functionalize the thermally expanded microspheres, and its measured tensile strength change rate was significantly different from that of Examples 5-7. In Examples 6-7, the tensile strength, notched impact strength, and initial thermal decomposition temperature were lower than those in Examples 5-7, while the water absorption rate was higher. This indicates that silane modification and polysiloxane coating are beneficial to improving the mechanical properties, heat resistance, and water resistance of the material. Furthermore, the notched impact strength in Comparative Example 7 was found to be significantly lower than that in Comparative Example 6. This is because the presence of the silver layer can effectively distribute the impact energy to a larger area, reducing the local stress concentration at the impact point. At the same time, the uniform distribution of functionalized thermal expansion microspheres inside the material better disperses the impact force, thereby enhancing the impact resistance of the material.

[0088] In the description of this specification, references to terms such as "an embodiment," "example," "specific example," etc., indicate that a specific feature, structure, material, or characteristic described in connection with that embodiment or example is included in at least one embodiment or example of the invention. In this specification, illustrative expressions of the above terms do not necessarily refer to the same embodiment or example. Furthermore, the specific features, structures, materials, or characteristics described may be combined in any suitable manner in one or more embodiments or examples.

[0089] The foregoing has shown and described the basic principles, main features, and advantages of the present invention. Those skilled in the art should understand that the present invention is not limited to the above embodiments. The embodiments and descriptions in the specification are merely illustrative of the principles of the invention. Various changes and modifications can be made to the invention without departing from its spirit and scope, and all such changes and modifications fall within the scope of the claimed invention.

Claims

1. An aging-resistant, foamed, high-gloss engineering plastic, characterized in that, It comprises the following components by weight: 100 parts ABS resin, 10-25 parts microcapsule foaming masterbatch, 0.5-2 parts nucleating agent, 0.1-1 part lubricant, and 0.1-0.6 parts antioxidant; The preparation method of the microcapsule foaming masterbatch is as follows: ABS resin and functionalized thermal expansion microspheres are mixed evenly at a mass ratio of 9:1, and then further mixed evenly on a two-roll mill, wherein the front roll temperature and the rear roll temperature are 80℃ and 85℃ respectively, and then crushed into granules in a high-speed crusher. The functionalized thermal expansion microspheres are prepared by using hydroxylamine to modify thermal expansion microspheres to introduce active sites on the surface of thermal expansion microspheres and then chemically plating silver to obtain silver-coated thermal expansion microspheres. Subsequently, mercaptopropyltrimethoxysilane is used to modify the silver-coated thermal expansion microspheres, and then the prepared silane-modified silver-coated thermal expansion microspheres are reacted with hydroxyl silicone oil to form the microspheres. The thermally expandable microspheres are prepared by suspension polymerization using isopentane as a foaming agent, acrylonitrile, methyl methacrylate, butyl methacrylate, vinyl light-stabilizing monomer, hydroxyethyl methacrylate as comonomers, and magnesium hydroxide as a dispersant; the vinyl light-stabilizing monomer is prepared by esterification reaction of 2-(2-hydroxy-5-benzyl)benzotriazole with acryloyl chloride.

2. The aging-resistant foamed high-gloss engineering plastic according to claim 1, characterized in that, The nucleating agent is one or a combination of several of organomontmorillonite, nano-calcium carbonate, silica, and nano-talc; the lubricant is one or a combination of several of pentaerythritol stearate, N,N'-ethylene bis-stearamide, and glyceryl monooleate; and the antioxidant is one or a combination of two of antioxidant 1076 and antioxidant 168.

3. The aging-resistant foamed high-gloss engineering plastic according to claim 1, characterized in that, The preparation method of the functionalized thermally expandable microspheres includes the following steps: A. Prepare an aqueous solution of hydroxylamine with a concentration of 1~1.5mol / L, then add thermally expanded microspheres, and stir the mixture at 65~70℃ for 10~15min. After the reaction is complete, wash and filter to obtain hydroxylamine-modified thermally expanded microspheres. B. Take silver nitrate in deionized water, mix well, and then add ammonia dropwise until a clear and transparent solution is obtained. Then, adjust the pH of the solution to 12-12.5 using sodium hydroxide solution, and continue to slowly add ammonia dropwise until the solution is clear and transparent to obtain silver ammonia solution. C. Add hydroxylamine-modified thermally expandable microspheres to freshly prepared silver ammonia solution and stir at room temperature for 3 hours. Then add glucose aqueous solution dropwise, controlling the dropwise addition rate to 0.5~1 drop / s. After the addition is complete, continue the reaction for 2 hours. After the reaction is complete, wash, filter and dry to obtain silver-coated thermally expandable microspheres. D. Disperse the silver-coated thermal expansion microspheres in anhydrous ethanol, then add mercaptopropyltrimethoxysilane, and stir the reaction under a nitrogen atmosphere for 6-8 hours. After the reaction is completed, wash with anhydrous ethanol, filter and dry to obtain silane-modified silver-coated thermal expansion microspheres. E. Disperse silane-modified silver-coated thermal expansion microspheres in isopropanol, heat to 50°C under nitrogen atmosphere, then add hydroxyl silicone oil and stannous isooctanoate and react for 2-4 hours. After the reaction is complete, filter to remove the solvent, wash the unreacted material with petroleum ether and ethylene glycol and vacuum dry to obtain functionalized thermal expansion microspheres.

4. The aging-resistant foamed high-gloss engineering plastic according to claim 3, characterized in that, The addition ratio of silver nitrate, deionized water, hydroxylamine-modified thermal expansion microspheres, and glucose aqueous solution is 0.4g:30mL:0.1g:20mL; the concentration of the glucose aqueous solution is 0.12~0.13g / mL.

5. The aging-resistant foamed high-gloss engineering plastic according to claim 3, characterized in that, The viscosity of the hydroxyl silicone oil is 3000 cs; the mass ratio of the silane-modified silver-coated thermal expansion microspheres, the hydroxyl silicone oil, and the stannous isooctanoate is 4~7:10~12:0.1~0.

15.

6. The aging-resistant foamed high-gloss engineering plastic according to claim 3, characterized in that, The method for preparing the thermally expandable microspheres includes the following steps: (1) Take magnesium hydroxide, polyvinylpyrrolidone, sodium nitrite and sodium chloride and add them to deionized water in sequence, stir to dissolve, and then stir at 1000 r / min for 5 min to obtain the aqueous phase; (2) Take isopentane, acrylonitrile, methyl methacrylate, butyl methacrylate, vinyl light-stabilized monomer, hydroxyethyl methacrylate, benzoyl peroxide, and dipropylene phthalate and mix them thoroughly to obtain the oil phase of suspension polymerization; (3) The oil phase is slowly added dropwise to the aqueous phase, and the stirring speed is maintained at 1000 r / min for 5 min to obtain an oil-in-water suspension; (4) Pour the suspension dispersion into the reactor, purge with nitrogen three times to remove oxygen, pressurize to 0.48~0.5MPa under nitrogen atmosphere and seal, set the polymerization stirring speed to 400r / min, and react at a constant temperature of 70℃ for 20h. After the reaction is completed, cool to room temperature, depressurize and discharge the material, filter, wash and dry to obtain thermally expanded microspheres.

7. The aging-resistant foamed high-gloss engineering plastic according to claim 6, characterized in that, In step (1), the mass ratio of magnesium hydroxide, polyvinylpyrrolidone, sodium nitrite and sodium chloride is 7.2~7.8:0.25~0.3:0.06~0.075:

30.

8. The aging-resistant foamed high-gloss engineering plastic according to claim 6, characterized in that, The preparation method of the vinyl light-stabilized monomer in step (2) includes the following steps: 2-(2-hydroxy-5-benzyl)benzotriazole, methylhydroquinone and triethylamine are placed in a reactor, tetrahydrofuran solvent is added, the mixture is heated to 55~65℃ and stirred until homogeneous, and then a mixed solution of acryloyl chloride and tetrahydrofuran is added dropwise. After the addition is completed, the mixture is stirred for 9~10h. After the reaction is completed, the tetrahydrofuran layer is removed with a separatory funnel, deionized water is added and stirred, then filtered, the solvent is removed by rotary evaporation and recrystallized with ethanol to obtain the vinyl light-stabilized monomer.

9. The aging-resistant foamed high-gloss engineering plastic according to claim 6, characterized in that, In step (2), the mass ratio of isopentane, acrylonitrile, methyl methacrylate, butyl methacrylate, vinyl light-stabilized monomer, hydroxyethyl methacrylate, benzoyl peroxide, and diallyl phthalate is 3:2:5:1:1~2:1:0.05:0.

03.

10. A preparation process for the aging-resistant foamed high-gloss engineering plastic according to any one of claims 1 to 9, characterized in that, Includes the following steps: S1. Weigh each component according to the weight parts, mix ABS resin, nucleating agent, lubricant and antioxidant, and then extrude and granulate. The extrusion temperature is 180~200℃ to obtain the mixture. S2. After mixing the mixture with the microcapsule foaming masterbatch, the mixture is injected into the molded material using an injection molding machine at a temperature of 190~210℃ to obtain an aging-resistant foamed high-gloss engineering plastic.

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