Low-odor PC / ABS alloy and preparation method thereof

Abstract

The invention discloses a low-odor PC / ABS alloy and a preparation method thereof, and belongs to the technical field of alloy materials, the alloy material comprises the following components by weight: 65-75 parts of PC resin, 25-35 parts of ABS resin, 2-8 parts of lanthanum modified diatomite, 3-5 parts of a compatilizer, 0.5-2 parts of a POSS-based deodorant, and 0.1-0.5 part of an initiator; the POSS-based deodorant is a polyhedral oligomeric silsesquioxane derivative, the molecular structure of the POSS-based deodorant contains a vinyl group, an epoxy group and a siloxane group at the same time, through the synergistic effect of the POSS-based deodorant and the lanthanum-modified diatomite, a multi-target deodorization system for generation inhibition, chemical capture and physical adsorption is constructed, the mechanical property of the PC / ABS alloy is maintained, and meanwhile the mechanical property of the PC / ABS alloy is improved. Source inhibition and whole-process control of VOC are achieved, the odor grade and the TVOC release amount are greatly reduced, and the long-acting and stable low-odor effect is achieved.

Description

Technical Field

[0001] This invention belongs to the field of alloy materials technology, specifically relating to a low-odor PC / ABS alloy and its preparation method. Background Technology

[0002] PC / ABS alloys combine the advantages of both PC and ABS: PC's high strength, high heat distortion temperature, and excellent dimensional stability significantly improve the material's mechanical properties and thermal stability; while ABS ensures the material's ease of processing and impact resistance. Therefore, PC / ABS alloys are widely used in automotive trim, lighting systems, home appliances, communication equipment, cameras, medical equipment, computers, construction, aerospace, and fiber optics.

[0003] However, with the popularization of automobiles, vehicles are closely related to daily life, and the air quality inside the car is receiving increasing attention and importance from consumers and automobile manufacturers. The plastic parts of automobile interiors are developing towards a green, environmentally friendly and healthy trend, and the production of environmentally friendly low-VOC materials for automobiles has become an inevitable trend. As an important material used in automobile interior parts, PC / ABS alloy has the following sources of VOC: (1) small molecules such as monomers (e.g., styrene, acrylonitrile), emulsifiers, and compatibilizers remaining in the raw materials during the synthesis stage; (2) volatilization or decomposition products of processing aids added during the modification of PC / ABS alloy; (3) thermo-oxidative degradation products of the rubber component in ABS copolymer under heat melting and high-speed shearing of the screw; (4) phenolic compounds generated by hydrolysis of the hydroxyl groups at the end of the polycarbonate molecular chain under high-temperature processing conditions.

[0004] To address the aforementioned issues, existing technologies primarily employ the following methods: First, adding fragrances to mask odors. While this can improve sensory comfort to some extent, it does not substantially reduce the release of volatile organic compounds (VOCs) and may even introduce new volatile components. Second, introducing physical adsorbents (such as activated carbon, molecular sieves, and porous silicates) or porous barrier agents to reduce the concentration of free small molecules through physical adsorption. However, this method not only has limited deodorization effects but also suffers from poor compatibility between inorganic fillers and polymer matrices, easily leading to a decline in the mechanical properties of the materials. Therefore, existing technologies often rely on single deodorization methods, making it difficult to achieve comprehensive and long-term removal of VOCs from different sources and with different polarities. Summary of the Invention

[0005] One of the objectives of this invention is to provide a low-odor PC / ABS alloy to solve the problem that VOCs in PC / ABS alloys are difficult to reduce comprehensively and effectively in the long term in the prior art.

[0006] The second objective of this invention is to provide a method for preparing the aforementioned low-odor PC / ABS alloy.

[0007] The objective of this invention can be achieved through the following technical solutions: A low-odor PC / ABS alloy, comprising the following components by weight: 65-75 parts PC resin, 25-35 parts ABS resin, 2-8 parts lanthanum modified diatomaceous earth, 3-5 parts compatibilizer, 0.5-2 parts POSS-based deodorizer, and 0.1-0.5 parts initiator.

[0008] The POSS-based deodorizer is a cage-type silsesquioxane derivative, whose molecular structure contains vinyl groups, epoxy groups, and siloxane groups simultaneously.

[0009] In some possible implementations, the POSS-based deodorizer is prepared by partially epoxidizing octavinyl-POSS and then reacting it with trimethoxysilane via a hydrosilylation reaction.

[0010] In some possible implementations, the aforementioned low-odor PC / ABS alloy also includes 0.3-1 parts by weight of lubricant and 0.2-0.5 parts by weight of antioxidant.

[0011] In some possible implementations, the raw materials for preparing lanthanum-modified diatomite include diatomite, sodium hydroxide solution, and lanthanum chloride solution. The ratio of diatomite, sodium hydroxide solution, and lanthanum chloride solution is 2-6 g: 100 mL: 10-20 mL. The concentration of sodium hydroxide solution is 1-6 mol / L, and the concentration of lanthanum chloride solution is 0.2-0.5 mol / L.

[0012] In some possible implementations, the preparation steps of the lanthanum-modified diatomite are as follows: Diatomaceous earth was calcined in a muffle furnace at 400℃ for 2 hours, then removed and cooled to room temperature. It was then added to a sodium hydroxide solution and stirred at 80-90℃ for 2 hours. After cooling to room temperature, a lanthanum chloride solution was added and stirred at 60℃ for 24 hours. Finally, it was filtered, washed, and dried. The dried product was calcined in a muffle furnace at 400℃ for 2 hours and ground through a 50-mesh sieve to obtain lanthanum-modified diatomaceous earth.

[0013] Lanthanum-modified diatomaceous earth can be obtained by chemical precipitation to modify it with lanthanum. After modification, the surface roughness of the diatomaceous earth increases, its pore structure becomes more abundant, and the number of pores increases significantly, which is beneficial for the physical adsorption of volatile organic compounds (VOCs). Simultaneously, the lanthanum in the lanthanum-modified diatomaceous earth mainly exists in the form of rare earth oxides, which can complex with the polar groups in VOC molecules, further enhancing its chemical adsorption capacity for VOCs, thereby improving the overall odor-neutralizing effect.

[0014] In some possible implementations, the preparation steps of the POSS-based deodorizer are as follows: S1. Add m-chloroperoxybenzoic acid dichloromethane solution and octavinyl-POSS dichloromethane solution to the flask in sequence. Stir the reaction at 40°C for 24 h. After the reaction is completed, filter to remove insoluble matter. Wash the filtrate with buffer solution and then dry it with anhydrous magnesium sulfate. Finally, remove dichloromethane by rotary evaporation to obtain vinyl epoxide POSS. S2. Add vinyl epoxide POSS, trimethoxysilane and anhydrous toluene to a flask, stir well and then add isopropanol chloroplatinic acid solution dropwise. After the addition is complete, react at 100°C for 8-10 h, then cool to room temperature and stir for 12 h. Finally, remove anhydrous toluene by vacuum distillation to obtain POSS-based deodorizer.

[0015] In some possible implementations, the molar ratio of S1 intermediate chloroperoxybenzoic acid and octavinyl-POSS is 1:3, and the buffer is a phosphate buffer with a pH of 7.5.

[0016] In some possible implementations, the ratio of vinyl epoxidized POSS to trimethoxysilane in S2 is 6.65 g: 0.02-0.04 mol, the amount of isopropanol chloroplatinate solution is 0.1-0.5% of the total mass of vinyl epoxidized POSS and trimethoxysilane, and the mass fraction of isopropanol chloroplatinate solution is 0.1-0.2%.

[0017] This invention uses octavinyl-POSS as raw material and m-chloroperoxybenzoic acid as oxidant to convert some vinyl groups of octavinyl-POSS into epoxy groups, thereby obtaining vinyl epoxide POSS. Then, a hydrosilylation reaction is used to obtain a POSS-based deodorizer containing vinyl groups, epoxy groups, and siloxane groups.

[0018] During the processing of PC / ABS alloy materials, the siloxane groups in the POSS-based deodorizer can undergo a coupling reaction with the active sites on the surface of lanthanum-modified diatomaceous earth to form an organic modification layer on the surface of diatomaceous earth. By utilizing the low surface energy characteristics of POSS, the interfacial tension between lanthanum-modified diatomaceous earth and PC / ABS resin matrix can be reduced, and the interfacial bonding between inorganic fillers and organic matrix can be improved, thereby reducing the decline in mechanical properties caused by interfacial defects. Meanwhile, the cage-like structure of POSS is dispersed at the nanoscale in the matrix, which helps to absorb and disperse impact energy, thereby maintaining or improving the mechanical properties of the alloy; the Si-O-Si bonds in the POSS skeleton have high thermal stability, which can delay the thermal decomposition of PC resin during the processing of PC / ABS alloy and reduce the release of VOCs caused by thermal degradation. Furthermore, the vinyl groups in POSS-based deodorizers, under the action of an initiator, can undergo copolymerization reactions with residual unsaturated monomers (such as styrene and acrylonitrile) in the alloy raw materials, chemically bonding them into the polymer network, thereby inhibiting the release of residual monomers from the source. The epoxy groups in POSS-based deodorizers can undergo ring-opening reactions with the terminal hydroxyl groups of PC resin. This reaction can, on the one hand, end-cap the PC, inhibiting the hydrolytic degradation of PC caused by metal salt impurities or residual moisture, and improving the thermal stability of the alloy during processing; on the other hand, it can promote the interfacial compatibility between the PC phase and the ABS phase, stabilize the phase structure of the alloy, and thus reduce VOC release caused by phase interface defects. In summary, the POSS-based deodorizer described in this invention, through the synergistic effect of multiple mechanisms, reduces VOC release from PC / ABS alloys while maintaining the material's good mechanical properties.

[0019] In some possible implementations, the PC resin is a bisphenol A type polycarbonate with a weight-average molecular weight of 17,000-30,000 g / mol and a glass transition temperature of 145-150 °C.

[0020] In some possible implementations, the ABS resin is a bulk ABS material with a weight-average molecular weight of 80,000-150,000 g / mol.

[0021] In some possible implementations, the initiator is dicumyl peroxide.

[0022] In some possible implementations, the compatibilizer is ABS-grafted maleic anhydride (ABS-g-MAH) and / or POE-grafted maleic anhydride (POE-g-MAH).

[0023] In some possible implementations, the lubricant is at least one of pentaerythritol stearate, silicone powder, and ethylene bis-stearamide.

[0024] In some possible implementations, the antioxidant is at least one of antioxidant 168, antioxidant 1010, antioxidant 1098, and antioxidant 1076.

[0025] The preparation method of the above-mentioned low-odor PC / ABS alloy includes the following steps: According to the formula, the raw materials are mixed evenly and then added to a twin-screw extruder. After melt blending and extrusion granulation, a low-odor PC / ABS alloy is obtained.

[0026] In some possible implementations, the twin-screw extruder has a barrel rotation speed of 200-300 rpm and a barrel temperature of 220-260°C.

[0027] The beneficial effects of this invention are: 1. This invention provides a low-odor PC / ABS alloy. Through the synergistic effect of a POSS-based deodorizer and lanthanum-modified diatomaceous earth, a multi-target deodorization system is constructed, encompassing inhibition of odor generation, chemical capture, and physical adsorption. While maintaining the mechanical properties of the PC / ABS alloy, it achieves source inhibition and full-process control of VOCs, significantly reducing odor levels and TVOC emissions, resulting in a long-lasting and stable low-odor effect. This material exhibits excellent comprehensive performance, meeting the application requirements of high environmental protection fields such as automotive interiors, and possesses promising market prospects and industrialization value.

[0028] 2. In this invention, the diatomaceous earth, after being modified with lanthanum, exhibits increased surface roughness and a richer pore structure, which is beneficial for the physical adsorption of VOCs. Simultaneously, the modified rare earth oxides can complex with the polar groups in VOCs, further enhancing the chemical adsorption capacity and thus improving the overall odor-neutralizing effect.

[0029] 3. In this invention, the POSS-based deodorizer is coupled with lanthanum-modified diatomaceous earth through siloxane groups, which improves interfacial bonding and reduces mechanical property loss; the cage-like structure is dispersed in the matrix at the nanoscale to absorb impact energy and maintain alloy toughness; the Si-O-Si skeleton delays the thermal decomposition of PC and inhibits VOC generation; the vinyl groups carried by the POSS-based deodorizer capture residual monomers under the action of the initiator, eliminating VOCs from the source; the epoxy groups react with the hydroxyl groups at the PC end, inhibiting hydrolysis and promoting PC / ABS compatibility. Detailed Implementation

[0030] 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.

[0031] Obviously, the following description is merely some examples or embodiments of this application. Those skilled in the art can apply this application to other similar scenarios without any inventive effort. Furthermore, it is understood that although the effort involved in such development may be complex and lengthy, for those skilled in the art related to the content disclosed in this application, any changes to design, manufacturing, or production based on the technical content disclosed in this application are merely conventional technical means and should not be construed as insufficient disclosure of the content of this application.

[0032] However, there may be instances where unnecessary detailed descriptions are omitted. For example, detailed descriptions of well-known matters or repetitive descriptions of essentially the same structure may be omitted. This is to avoid making the following description unnecessarily lengthy and to facilitate understanding by those skilled in the art. Furthermore, the following description is provided to enable those skilled in the art to fully understand this application and is not intended to limit the subject matter of the claims.

[0033] Unless otherwise specified, all embodiments and optional embodiments of this application can be combined to form new technical solutions, and all technical features and optional technical features of this application can be combined to form new technical solutions.

[0034] Existing solutions for the high odor of PC / ABS alloys involve two main approaches: first, adding fragrances to mask the odor. While this can improve sensory comfort to some extent, it doesn't substantially reduce the release of volatile organic compounds (VOCs) and may even introduce new volatile components; second, introducing physical adsorbents (such as activated carbon, molecular sieves, and porous silicates) or porous barrier agents to reduce the concentration of free small molecules through physical adsorption. However, this approach has limited odor removal effectiveness, and the poor compatibility between inorganic fillers and the polymer matrix can easily lead to a decline in the material's mechanical properties. Therefore, existing technologies often employ single odor removal methods and still struggle to achieve comprehensive and long-term removal of VOCs from different sources and with different polarities.

[0035] In this regard, the first aspect of the embodiments of this application provides a low-odor PC / ABS alloy, which, by weight, comprises the following components: 65-75 parts PC resin, 25-35 parts ABS resin, 2-8 parts lanthanum modified diatomaceous earth, 3-5 parts compatibilizer, 0.5-2 parts POSS-based deodorizer, and 0.1-0.5 parts initiator.

[0036] The POSS-based deodorizer is a cage-type silsesquioxane derivative, whose molecular structure contains vinyl groups, epoxy groups, and siloxane groups simultaneously.

[0037] In some specific embodiments, the POSS-based deodorizer is prepared by partially epoxidizing octavinyl-POSS and then reacting it with trimethoxysilane via a hydrosilylation reaction.

[0038] In some specific embodiments, the aforementioned low-odor PC / ABS alloy further includes 0.3-1 parts by weight of lubricant and 0.2-0.5 parts by weight of antioxidant.

[0039] In some specific embodiments, the raw materials for preparing lanthanum-modified diatomite include diatomite, sodium hydroxide solution, and lanthanum chloride solution. The ratio of diatomite, sodium hydroxide solution, and lanthanum chloride solution is 2-6g:100mL:10-20mL. The concentration of sodium hydroxide solution is 1-6mol / L, and the concentration of lanthanum chloride solution is 0.2-0.5mol / L.

[0040] In some specific embodiments, the preparation steps of the lanthanum-modified diatomite are as follows: Diatomaceous earth was calcined in a muffle furnace at 400℃ for 2 hours, then removed and cooled to room temperature. It was then added to a sodium hydroxide solution and stirred at 80-90℃ for 2 hours. After cooling to room temperature, a lanthanum chloride solution was added and stirred at 60℃ for 24 hours. Finally, it was filtered, washed, and dried. The dried product was calcined in a muffle furnace at 400℃ for 2 hours and ground through a 50-mesh sieve to obtain lanthanum-modified diatomaceous earth.

[0041] In some specific embodiments, the preparation steps of the POSS-based deodorizer are as follows: S1. Add m-chloroperoxybenzoic acid dichloromethane solution and octavinyl-POSS dichloromethane solution to the flask in sequence. Stir the reaction at 40°C for 24 h. After the reaction is completed, filter to remove insoluble matter. Wash the filtrate with buffer solution and then dry it with anhydrous magnesium sulfate. Finally, remove dichloromethane by rotary evaporation to obtain vinyl epoxide POSS. S2. Add vinyl epoxide POSS, trimethoxysilane and anhydrous toluene to a flask, stir well and then add isopropanol chloroplatinic acid solution dropwise. After the addition is complete, react at 100°C for 8-10 h, then cool to room temperature and stir for 12 h. Finally, remove anhydrous toluene by vacuum distillation to obtain POSS-based deodorizer.

[0042] In some specific embodiments, the molar ratio of S1 intermediate chloroperoxybenzoic acid and octavinyl-POSS is 1:3, and the buffer solution is a phosphate buffer with a pH of 7.5.

[0043] In some specific embodiments, the ratio of vinyl epoxidized POSS to trimethoxysilane in S2 is 6.65g:0.02-0.04mol, the amount of isopropanol chloroplatinate solution is 0.1-0.5% of the total mass of vinyl epoxidized POSS and trimethoxysilane, and the mass fraction of isopropanol chloroplatinate solution is 0.1-0.2%.

[0044] In some specific embodiments, the PC resin is a bisphenol A type polycarbonate with a weight-average molecular weight of 17,000-30,000 g / mol and a glass transition temperature of 145-150°C.

[0045] In some specific embodiments, the ABS resin is bulk ABS material with a weight-average molecular weight of 80,000-150,000 g / mol.

[0046] In some specific embodiments, the initiator is dicumyl peroxide.

[0047] In some specific embodiments, the compatibilizer is ABS-grafted maleic anhydride (ABS-g-MAH) and / or POE-grafted maleic anhydride (POE-g-MAH).

[0048] In some specific embodiments, the lubricant is at least one of pentaerythritol stearate, silicone powder, and ethylene bis-stearamide.

[0049] In some specific embodiments, the antioxidant is at least one of antioxidant 168, antioxidant 1010, antioxidant 1098, and antioxidant 1076.

[0050] The second aspect of this application describes a method for preparing the aforementioned low-odor PC / ABS alloy, comprising the following steps: According to the formula, the raw materials are mixed evenly and then added to a twin-screw extruder. After melt blending and extrusion granulation, a low-odor PC / ABS alloy is obtained.

[0051] In some specific embodiments, the barrel speed of the twin-screw extruder is 200-300 rpm, and the barrel temperature is 220-260℃.

[0052] The following is a detailed description with reference to specific examples.

[0053] In the embodiments and comparative examples of this application, the PC resin is Covestro's PC-2600; the ABS resin is INEOS Styrol's GP-22; and the ABS grafted with maleic anhydride is a product of Dongguan Shenghao Plastic Raw Materials Co., Ltd.

[0054] Preparation Example 1

[0055] A POSS-based deodorizer, whose molecular structure simultaneously contains vinyl groups, epoxy groups, and siloxane groups, is prepared as follows: S1. Dissolve 0.05 mol of m-chloroperoxybenzoic acid in 50 mL of dichloromethane to obtain mixed solution a; dissolve 0.15 mol of octavinyl-POSS in 150 mL of dichloromethane to obtain mixed solution b; add solutions a and b sequentially to a reaction flask and stir at 40 °C for 24 h. After the reaction is complete, filter to remove insoluble matter, wash the filtrate with phosphate buffer solution at pH 7.5, dry with anhydrous magnesium sulfate, and finally remove dichloromethane by rotary evaporation to obtain vinyl epoxide POSS; S2. Add 33.25g of vinyl epoxidized POSS, 0.1mol of trimethoxysilane and 400mL of anhydrous toluene to a flask, stir well, and then add dropwise a 0.1% isopropanol chloroplatinate solution. The amount of isopropanol chloroplatinate solution is 0.1% of the total mass of vinyl epoxidized POSS and trimethoxysilane. After the addition is complete, react at 100℃ for 8h, then cool to room temperature and stir for 12h. Finally, remove the anhydrous toluene by vacuum distillation to obtain the POSS-based deodorizer.

[0056] Preparation Example 2

[0057] A POSS-based deodorizer, whose molecular structure simultaneously contains vinyl groups, epoxy groups, and siloxane groups, is prepared as follows: S1. Dissolve 0.05 mol of m-chloroperoxybenzoic acid in 100 mL of dichloromethane to obtain mixed solution a; dissolve 0.15 mol of octavinyl-POSS in 200 mL of dichloromethane to obtain mixed solution b; add solutions a and b sequentially to a reaction flask and stir at 40 °C for 24 h. After the reaction is complete, filter to remove insoluble matter, wash the filtrate with phosphate buffer solution at pH 7.5, dry with anhydrous magnesium sulfate, and finally remove dichloromethane by rotary evaporation to obtain vinyl epoxide POSS; S2. Add 33.25g of vinyl epoxidized POSS, 0.2mol of trimethoxysilane and 450mL of anhydrous toluene to a flask, stir well, and then add dropwise a 0.2% isopropanol chloroplatinate solution. The amount of isopropanol chloroplatinate solution is 0.5% of the total mass of vinyl epoxidized POSS and trimethoxysilane. After the addition is complete, react at 100℃ for 10h, then cool to room temperature and stir for 12h. Finally, remove the anhydrous toluene by vacuum distillation to obtain the POSS-based deodorizer.

[0058] Preparation Example 3

[0059] A POSS-based deodorizer, whose molecular structure simultaneously contains vinyl groups, epoxy groups, and siloxane groups, is prepared as follows: S1. Dissolve 0.05 mol of m-chloroperoxybenzoic acid in 80 mL of dichloromethane to obtain mixed solution a; dissolve 0.15 mol of octavinyl-POSS in 180 mL of dichloromethane to obtain mixed solution b; add solutions a and b sequentially to a reaction flask and stir at 40 °C for 24 h. After the reaction is complete, filter to remove insoluble matter, wash the filtrate with phosphate buffer solution at pH 7.5, dry with anhydrous magnesium sulfate, and finally remove dichloromethane by rotary evaporation to obtain vinyl epoxide POSS; S2. Add 33.25g of vinyl epoxidized POSS, 0.15mol of trimethoxysilane and 430mL of anhydrous toluene to a flask, stir well, and then add dropwise a 0.15% isopropanol chloroplatinate solution. The amount of isopropanol chloroplatinate solution is 0.3% of the total mass of vinyl epoxidized POSS and trimethoxysilane. After the addition is complete, react at 100℃ for 9h, then cool to room temperature and stir for 12h. Finally, remove the anhydrous toluene by vacuum distillation to obtain the POSS-based deodorizer.

[0060] Compare with Example 1

[0061] This comparative example is vinyl epoxide POSS, whose molecular structure contains vinyl groups and epoxy groups, but does not contain siloxane groups. The preparation process of vinyl epoxide POSS is the same as that of preparation example 1.

[0062] Compare with Example 2

[0063] A POSS-based deodorizer, whose molecular structure contains vinyl groups and siloxane groups but no epoxy groups, is prepared as follows: 0.1 mol octavinyl-POSS, 0.1 mol trimethoxysilane, and 400 mL anhydrous toluene were added to a flask and stirred until homogeneous. Then, a 0.1% isopropanol chloroplatinate solution was added dropwise. The amount of isopropanol chloroplatinate solution was 0.1% of the sum of the masses of vinyl epoxidized POSS and trimethoxysilane. After the addition was complete, the mixture was reacted at 100 °C for 8 h, then cooled to room temperature and stirred for 12 h. Finally, the anhydrous toluene was removed by vacuum distillation to obtain the POSS-based deodorizer.

[0064] Compare with Example 3

[0065] This comparative example is octavinyl-POSS, whose molecular structure contains only vinyl groups and no epoxy groups or siloxane groups.

[0066] Example 1

[0067] A low-odor PC / ABS alloy, comprising the following components by weight: 65 parts PC resin, 35 parts ABS resin, 2 parts lanthanum modified diatomaceous earth, 3 parts ABS grafted maleic anhydride, 0.5 parts POSS-based deodorizer of Preparation Example 1, 0.1 parts dicumyl peroxide, 0.3 parts pentaerythritol stearate, and 0.2 parts antioxidant 168.

[0068] The preparation steps for lanthanum-modified diatomite are as follows: 2g of diatomaceous earth was calcined in a muffle furnace at 400℃ for 2h. After cooling to room temperature, it was added to 100mL of 1mol / L sodium hydroxide solution and stirred at 80℃ for 2h. After cooling to room temperature, 10mL of 0.2mol / L lanthanum chloride solution was added and stirred at 60℃ for 24h. Finally, it was filtered, washed, and dried. The dried product was calcined in a muffle furnace at 400℃ for 2h and ground through a 50-mesh sieve to obtain lanthanum-modified diatomaceous earth.

[0069] The preparation method of the above-mentioned low-odor PC / ABS alloy includes the following steps: According to the formula, the raw materials are mixed evenly and then added to a twin-screw extruder. The barrel speed is controlled at 200 rpm. After melt blending, extrusion and granulation, a low-odor PC / ABS alloy is obtained. The controlled temperatures of each section of the main barrel (from the feed port to the die outlet) are 200℃, 210℃, 220℃, 230℃, 240℃, 250℃, 260℃, 250℃, 240℃, and 230℃, respectively.

[0070] Example 2

[0071] A low-odor PC / ABS alloy, comprising the following components by weight: 70 parts PC resin, 30 parts ABS resin, 5 parts lanthanum modified diatomaceous earth, 4 parts ABS grafted maleic anhydride, 1 part POSS-based deodorizer of Preparation Example 1, 0.3 parts dicumyl peroxide, 0.5 parts pentaerythritol stearate, and 0.4 parts antioxidant 168.

[0072] The preparation steps for lanthanum-modified diatomite are the same as in Example 1.

[0073] The preparation method of the low-odor PC / ABS alloy is the same as in Example 1.

[0074] Example 3

[0075] A low-odor PC / ABS alloy, comprising the following components by weight: 75 parts PC resin, 25 parts ABS resin, 8 parts lanthanum modified diatomaceous earth, 5 parts ABS grafted maleic anhydride, 2 parts POSS-based deodorizer of Preparation Example 1, 0.5 parts dicumyl peroxide, 1 part pentaerythritol stearate, and 0.5 parts antioxidant 168.

[0076] The preparation steps for lanthanum-modified diatomite are the same as in Example 1.

[0077] The preparation method of the low-odor PC / ABS alloy is the same as in Example 1.

[0078] Example 4

[0079] A low-odor PC / ABS alloy, compared with Example 1, differs only in that the lanthanum-modified diatomaceous earth preparation steps in this example are as follows: 4g of diatomaceous earth was calcined in a muffle furnace at 400℃ for 2 hours. After cooling to room temperature, it was added to 100mL of 3mol / L sodium hydroxide solution and stirred at 85℃ for 2 hours. After cooling to room temperature, 15mL of 0.3mol / L lanthanum chloride solution was added and stirred at 60℃ for 24 hours. Finally, it was filtered, washed, and dried. The dried product was calcined in a muffle furnace at 400℃ for 2 hours and ground through a 50-mesh sieve to obtain lanthanum-modified diatomaceous earth.

[0080] Example 5

[0081] A low-odor PC / ABS alloy, compared with Example 1, differs only in that the lanthanum-modified diatomaceous earth preparation steps in this example are as follows: 6g of diatomaceous earth was calcined in a muffle furnace at 400℃ for 2h. After cooling to room temperature, it was added to 100mL of 6mol / L sodium hydroxide solution and stirred at 90℃ for 2h. After cooling to room temperature, 20mL of 0.5mol / L lanthanum chloride solution was added and stirred at 60℃ for 24h. Finally, it was filtered, washed, and dried. The dried product was calcined in a muffle furnace at 400℃ for 2h and ground through a 50-mesh sieve to obtain lanthanum-modified diatomaceous earth.

[0082] Example 6

[0083] A low-odor PC / ABS alloy, compared with Example 1, differs only in that the POSS-based deodorizer in Example 1 is replaced with an equal weight of the product obtained in Preparation Example 2.

[0084] Example 7

[0085] A low-odor PC / ABS alloy, compared with Example 1, differs only in that the POSS-based deodorizer in Example 1 is replaced with an equal weight of the product obtained in Preparation Example 3.

[0086] Example 8

[0087] A low-odor PC / ABS alloy, compared with Example 4, differs only in that the POSS-based deodorizer in Example 4 is replaced with an equal weight of the product obtained in Preparation Example 2.

[0088] Comparative Example 1

[0089] A low-odor PC / ABS alloy, compared with Example 1, differs only in that the POSS-based deodorizer in Example 1 is replaced with an equal weight of the substance in Comparative Example 1.

[0090] Comparative Example 2

[0091] A low-odor PC / ABS alloy, compared with Example 1, differs only in that the POSS-based deodorizer in Example 1 is replaced with an equal weight of the product prepared in Comparative Example 2.

[0092] Comparative Example 3

[0093] A low-odor PC / ABS alloy, compared with Example 1, differs only in that the POSS-based deodorizer in Example 1 is replaced with an equal weight of the substance in Comparative Example 3.

[0094] Comparative Example 4

[0095] A low-odor PC / ABS alloy, compared with Example 1, differs only in that the lanthanum-modified diatomite in Example 1 is replaced with an equal mass of calcined diatomite. The preparation steps of calcined diatomite are as follows: calcining the diatomite in a muffle furnace at 400°C for 2 hours, and then removing it and cooling it to room temperature.

[0096] Comparative Example 5

[0097] A low-odor PC / ABS alloy, which differs from Example 1 only in that dicumyl peroxide is removed from Example 1.

[0098] The low-odor PC / ABS alloys obtained in Examples 1-8 and Comparative Examples 1-5 were dried at 100°C for 4 hours. Standard mechanical test specimens were then injection molded. The temperature settings of each zone of the injection molding machine, from the feeding section to the nozzle, were 200°C, 250°C, 250°C, and 235°C. The injection pressure was 80±5MPa, the injection time was 15s, the holding time was 10s, and the cooling time was 25s. Performance tests were then conducted, and the test procedure is as follows: I. Odor Measurement: (1) The odor level was tested according to the PV3900 standard of Volkswagen AG, Germany. The test conditions were 80℃ for 2 hours. The evaluation was based on a 1-6 level. The higher the level, the stronger the odor. (2) The total carbon volatilization (total organic matter volatilization, TVOC) was determined according to TS-INT-002. II. Mechanical property testing: (1) Tensile strength was tested in accordance with GB / T10400.2-2006, with a tensile rate of 50 mm / min; (2) The notched impact strength was tested according to GB / T1843-2008. The notch of the specimen was type A, and the impact energy was 2.75J. The test results are shown in Table 1: Table 1. Performance test results of low-odor PC / ABS alloys in the examples and comparative examples.

[0099] Analysis of the data recorded in Table 1 shows that although the raw material components of Examples 1, 2 and 3 are the same, the amounts are different, resulting in differences in the odor level, TVOC and mechanical properties of the final PC / ABS alloy. Among them, the PC / ABS alloy described in Example 3 has the best odor. The test results of Examples 1, 4 and 5 show that by keeping the amount of lanthanum-modified diatomite constant while reasonably changing its preparation method, the odor level and mechanical properties of the final PC / ABS alloy will change. Among them, the PC / ABS alloys described in Examples 4 and 5 have better odor than those in Example 1. The test results of Examples 1, 6, 7 and 8 show that keeping the amount of POSS-based deodorizer constant while reasonably changing its preparation method will lead to changes in the odor level and mechanical properties of the final PC / ABS alloy. As can be seen from the test results of Example 1, Comparative Example 1, Comparative Example 2 and Comparative Example 3, changing the raw materials and preparation mechanism of POSS-based deodorizer will result in the POSS-based deodorizer molecular structure not containing vinyl groups, epoxy groups and siloxane groups at the same time, which will lead to its inability to play a good role in deodorizing and compressing, and ultimately the PC / ABS alloy odor level and mechanical properties will be significantly worse. The test results of Example 1 and Comparative Example 4 show that, compared with using calcined diatomite, using lanthanum-modified diatomite is more conducive to obtaining low-odor, high-performance PC / ABS alloys. As can be seen from the test results of Example 1 and Comparative Example 5, omitting the use of the initiator means that the vinyl groups of the POSS-based deodorizer cannot be activated, and the residual monomers in the raw materials are not captured by copolymerization, which will lead to a significant deterioration in the odor of the PC / ABS alloy. In summary, this invention utilizes the synergistic effect of POSS-based deodorizers and lanthanum-modified diatomaceous earth to construct a multi-target deodorization system that inhibits odor generation, chemically captures odors, and physically adsorbs them. While maintaining the mechanical properties of PC / ABS alloys, it achieves source suppression and full-process control of VOCs, significantly reducing odor levels and TVOC emissions, resulting in a long-lasting and stable low-odor effect. This material exhibits excellent comprehensive performance, meeting the application requirements of high environmental protection fields such as automotive interiors, and possesses promising market prospects and industrialization value.

[0100] It should be noted that, in this document, relational terms such as "first" and "second" are used only to distinguish one entity or operation from another, and do not necessarily require or imply any such actual relationship or order between these entities or operations. Furthermore, the terms "comprising," "including," or any other variations thereof are intended to cover non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements includes not only those elements but also other elements not expressly listed, or elements inherent to such process, method, article, or apparatus.

[0101] Although embodiments of the invention have been shown and described, it will be understood by those skilled in the art that various changes, modifications, substitutions and alterations can be made to these embodiments without departing from the principles and spirit of the invention, the scope of which is defined by the appended claims and their equivalents.

Claims

1. A low-odor PC / ABS alloy, characterized in that, By weight, it includes the following components: 65-75 parts PC resin, 25-35 parts ABS resin, 2-8 parts lanthanum-modified diatomaceous earth, 3-5 parts compatibilizer, 0.5-2 parts POSS-based deodorizer, and 0.1-0.5 parts initiator; The POSS-based deodorizer is a cage-type silsesquioxane derivative, whose molecular structure contains vinyl groups, epoxy groups, and siloxane groups simultaneously.

2. The low-odor PC / ABS alloy according to claim 1, characterized in that, The POSS-based deodorizer is prepared by partial epoxidation of octavinyl-POSS, followed by hydrosilylation reaction with trimethoxysilane.

3. The low-odor PC / ABS alloy according to claim 1, characterized in that, The low-odor PC / ABS alloy also includes 0.3-1 parts by weight of lubricant and 0.2-0.5 parts by weight of antioxidant.

4. The low-odor PC / ABS alloy according to claim 1, characterized in that, The preparation steps of the lanthanum-modified diatomite are as follows: Diatomaceous earth was calcined in a muffle furnace at 400℃ for 2 hours, then removed and cooled to room temperature. It was then added to a sodium hydroxide solution and stirred at 80-90℃ for 2 hours. After cooling to room temperature, a lanthanum chloride solution was added and stirred at 60℃ for 24 hours. Finally, it was filtered, washed, and dried. The dried product was calcined in a muffle furnace at 400℃ for 2 hours and ground through a 50-mesh sieve to obtain lanthanum-modified diatomaceous earth.

5. A low-odor PC / ABS alloy according to claim 1 or 2, characterized in that, The preparation steps of the POSS-based deodorizer are as follows: S1. Add m-chloroperoxybenzoic acid dichloromethane solution and octavinyl-POSS dichloromethane solution to the flask in sequence. Stir the reaction at 40°C for 24 h. After the reaction is completed, filter to remove insoluble matter. Wash the filtrate with buffer solution and then dry it with anhydrous magnesium sulfate. Finally, remove dichloromethane by rotary evaporation to obtain vinyl epoxide POSS. S2. Add vinyl epoxide POSS, trimethoxysilane and anhydrous toluene to a flask, stir well and then add isopropanol chloroplatinic acid solution dropwise. After the addition is complete, react at 100°C for 8-10 h, then cool to room temperature and stir for 12 h. Finally, remove anhydrous toluene by vacuum distillation to obtain POSS-based deodorizer.

6. The low-odor PC / ABS alloy according to claim 5, characterized in that, The molar ratio of S1 intermediate chloroperoxybenzoic acid and octavinyl-POSS is 1:3, and the buffer solution is a phosphate buffer with a pH of 7.

5.

7. The low-odor PC / ABS alloy according to claim 5, characterized in that, In S2, the ratio of vinyl epoxidized POSS to trimethoxysilane is 6.65 g: 0.02-0.04 mol, the amount of isopropanol chloroplatinate solution is 0.1-0.5% of the total mass of vinyl epoxidized POSS and trimethoxysilane, and the mass fraction of isopropanol chloroplatinate solution is 0.1-0.2%.

8. The low-odor PC / ABS alloy according to claim 1, characterized in that, The ABS resin is a bulk ABS material with a weight-average molecular weight of 80,000-150,000 g / mol.

9. A low-odor PC / ABS alloy according to claim 1, characterized in that, The initiator is dicumyl peroxide.

10. A method for preparing a low-odor PC / ABS alloy, characterized in that, The method for preparing the low-odor PC / ABS alloy according to any one of claims 1-9 comprises the following steps: According to the formula, the raw materials are mixed evenly and then added to a twin-screw extruder. After melt blending and extrusion granulation, a low-odor PC / ABS alloy is obtained.

Images