Thermoplastic resin composition and application
By preparing a thermoplastic resin composition containing phosphate ester, thioester and hindered phenol functional additives, the oxidation resistance and flammability problems of ABS materials in automotive interior parts are solved, efficient flame retardant and antioxidant effects are achieved, and the comprehensive performance of the material is improved.
Patent Information
- Application Number
- CN202510707818.5
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-05-29
- Publication Date
- 2025-09-05
- Estimated Expiration
- Not applicable · inactive patent
AI Technical Summary
ABS material has poor oxidation resistance in automotive interior parts, is prone to yellowing and brittleness, is flammable, and produces toxic gases when burned, which limits its application.
A thermoplastic resin composition is prepared by preparing a functional additive containing three functional groups: phosphate, thioester and hindered phenol, combined with a styrene-butadiene-acrylonitrile copolymer, a light stabilizer and a processing aid to improve the flame retardancy and antioxidant properties of the material.
It significantly improves the flame retardancy and oxidation resistance of the material, maintains excellent mechanical properties, and is suitable for automotive interior parts.
Smart Images
Figure BDA0005426293590000031 
Figure BDA0005426293590000041
Abstract
Description
Technical Field
[0001] The present invention belongs to the technical field of automobile interior decoration parts, and in particular relates to a thermoplastic resin composition and application thereof. Background Art
[0002] With the rapid development of new energy vehicles, the performance and quality requirements for automotive interior components are increasing. Thermoplastic resins, with their excellent moldability, recyclability, and diverse performance characteristics, also contribute to lightweighting vehicles, thereby reducing energy consumption and improving fuel economy. Furthermore, their excellent moldability can meet the design requirements of complex automotive parts, leading to their widespread application in automotive interior components.
[0003] Commonly used thermoplastic resins for automotive interior components include polypropylene (PP), acrylonitrile-butadiene-styrene copolymer (ABS), and polyamide (PA). ABS and ASA-based materials are excellent engineering plastics with high gloss, good impact toughness, creep resistance, a wide operating temperature range, excellent electrical insulation, good dimensional stability, and high reliability. Due to their excellent performance, they are often used in automotive interior components such as center consoles, buttons, knobs, air conditioning vents, decorative strips, door handles, and cup holders. However, ABS has poor oxidation resistance and tends to yellow and become brittle with long-term exposure to ultraviolet light. Furthermore, ABS is inherently flammable (UL94HB grade), producing black smoke and toxic gases such as hydrogen cyanide when burned. These two factors significantly limit ABS's application. Therefore, there is an urgent need to address these issues to meet the growing demands of automotive interior technology. Summary of the Invention
[0004] The purpose of the present invention is to overcome the defects of the prior art and provide a thermoplastic resin composition and application.
[0005] The purpose of the present invention can be achieved through the following technical solutions:
[0006] A thermoplastic resin composition is prepared by the following steps:
[0007] Styrene-butadiene-acrylonitrile copolymer, light stabilizer, functional additives and processing aids are added to a high-speed mixer and fully stirred to obtain a mixture, which is then added to a twin-screw extruder for melt blending, extrusion granulation and drying to obtain a thermoplastic resin composition.
[0008] As a further technical solution, the raw materials are calculated in parts by weight as follows: 71-85 parts of styrene-butadiene-acrylonitrile copolymer, 1.2-1.8 parts of light stabilizer, 4-12 parts of functional additives, and 3-6 parts of processing aids.
[0009] As a further technical solution, the light stabilizer is a hindered phenol light stabilizer.
[0010] As a further technical solution, the processing aid is one of polyethylene wax, EVA wax, oleamide and erucamide.
[0011] As a further technical solution, the rotation speed of the high-speed mixer is 1000-1500 r / min, and the stirring time is 15-30 min.
[0012] As a further technical solution, the drying condition is to dry in an oven at 80-100° C. for 12-24 hours.
[0013] As a further technical solution, the functional additive is prepared by the following steps:
[0014] Step A1, adding the reaction raw materials thiodiethanol and diethylphosphinoacetic acid to a three-necked flask equipped with a magnetic stirrer, a condenser and a thermometer, then adding toluene, stirring at room temperature for 30-60 minutes, then adding p-toluenesulfonic acid, heating the oil bath to 80° C., reacting for 6-8 hours, and after the reaction is complete, cooling to room temperature, filtering, washing the organic phase with saturated sodium bicarbonate solution until neutral, drying over anhydrous sodium sulfate, rotary evaporation to remove toluene, and purifying by column chromatography (petroleum ether / ethyl acetate = 3:1) to obtain the first product;
[0015] As a further technical solution, in step A1, the ratio of thiodiethanol, diethylphosphinoacetic acid, toluene, and p-toluenesulfonic acid is 13.7 g:19.6 g:100 mL:0.8 g.
[0016] In step A1, thiodiethanol and diethylphosphinoacetic acid undergo an esterification reaction under the catalysis of p-toluenesulfonic acid. The molar ratio of the two is regulated to be 1:1, and thiodiethanol is slightly excessive to reduce side reactions. The reaction formula is as follows:
[0017]
[0018] Step A2, adding the first product of the reaction raw material and β-(3,5-di-tert-butyl-4-hydroxyphenyl) propionyl chloride to a three-necked flask equipped with a magnetic stirrer, a condenser and a thermometer, then adding toluene, stirring at room temperature for 15-20 minutes, then adding triethylamine (acid binding agent), and then placing the device in a 45-55°C water bath, reacting in a constant temperature water bath for 3-5 hours. After the reaction is complete, filtering, rotary evaporation is performed on a rotary evaporator, and purification by column chromatography (petroleum ether / ethyl acetate = 5:1) to obtain a functional additive;
[0019] As a further technical solution, the ratio of the first product, β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionyl chloride, toluene, and triethylamine used in step A2 is 29.9 g:29.6 g:150 mL:10.1 g.
[0020] In step A2, the first product undergoes an acylation reaction with β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionyl chloride under the catalysis of triethylamine. The reaction formula is as follows:
[0021]
[0022] The present invention prepares a functional additive through a two-step reaction. The functional additive molecule contains three functional groups: phosphate, thioester and hindered phenol. Among them, phosphate is a phosphorus-based flame retardant, which can achieve flame retardancy through dual pathways of gas-phase free radical termination and condensed-phase carbonization, thereby improving the flame retardant performance of a matrix. In addition, thioester and hindered phenol are both antioxidant functional groups, and thioester, as an auxiliary antioxidant, can synergize with the main antioxidant hindered phenol, thereby greatly enhancing the antioxidant performance of the matrix. Moreover, the three functions are specifically integrated into one, and compared with single-functional additives, the homogeneity is good and the influence on the mechanical properties of the matrix is small.
[0023] Beneficial effects of the present invention:
[0024] 1. The thermoplastic resin composition prepared by the present invention uses ABS as a matrix, which gives the material excellent mechanical properties;
[0025] 2. Adding hindered amine light stabilizers to the raw materials of the present invention can improve the oxidation resistance of the material under ultraviolet light and improve the antioxidant performance of the material;
[0026] 3. The raw materials of the present invention are added with self-made functional additives, which contain three functional groups and can greatly improve the antioxidant and flame retardant properties of the material;
[0027] In summary, the thermoplastic resin composition prepared in the present invention has excellent mechanical properties, high flame retardancy and antioxidant properties, and has important application value in the field of automotive interior parts technology. DETAILED DESCRIPTION
[0028] The following will be combined with the embodiments of the present invention to clearly and completely describe the technical solutions in the embodiments of the present invention. Obviously, the embodiments described are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without making any creative efforts shall fall within the scope of protection of the present invention.
[0029] Example 1
[0030] Preparation of functional additives:
[0031] Step A1, 13.7g of thiodiethanol and 19.6g of diethylphosphinoacetic acid were added to a three-necked flask equipped with a magnetic stirrer, a condenser and a thermometer, and 100mL of toluene was added. The mixture was stirred at room temperature for 30min, and then 0.8g of p-toluenesulfonic acid was added. The oil bath was heated to 80°C and reacted for 6h. After the reaction was completed, the mixture was cooled to room temperature, filtered, and the organic phase was washed with saturated sodium bicarbonate solution until neutral, dried over anhydrous sodium sulfate, and the toluene was removed by rotary evaporation. The mixture was purified by column chromatography (petroleum ether / ethyl acetate = 3:1) to obtain the first product;
[0032] Step A2, 29.9g of the first product and 29.6g of β-(3,5-di-tert-butyl-4-hydroxyphenyl) propionyl chloride were added to a three-necked flask equipped with a magnetic stirrer, a condenser and a thermometer, and then 150mL of toluene was added. The mixture was stirred at room temperature for 15min, and then 10.1g of triethylamine was added. The apparatus was placed in a 45°C water bath and reacted under a constant temperature water bath for 3h. After the reaction was completed, the mixture was filtered, evaporated in a rotary evaporator, and purified by column chromatography (petroleum ether / ethyl acetate = 5:1) to obtain a functional additive.
[0033] Example 2
[0034] Preparation of functional additives:
[0035] Step A1, 27.4g of thiodiethanol and 39.2g of diethylphosphinoacetic acid were added to a three-necked flask equipped with a magnetic stirrer, a condenser and a thermometer, and 200mL of toluene was added. The mixture was stirred at room temperature for 60min, and then 1.6g of p-toluenesulfonic acid was added. The oil bath was heated to 80°C and reacted for 8h. After the reaction was completed, the mixture was cooled to room temperature, filtered, and the organic phase was washed with saturated sodium bicarbonate solution until neutral, dried over anhydrous sodium sulfate, and the toluene was removed by rotary evaporation. The mixture was purified by column chromatography (petroleum ether / ethyl acetate = 3:1) to obtain the first product;
[0036] Step A2, 59.8g of the first product and 59.2g of β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionyl chloride were added to a three-necked flask equipped with a magnetic stirrer, a condenser and a thermometer, and then 300mL of toluene was added. The mixture was stirred at room temperature for 20min, and then 20.2g of triethylamine was added. The apparatus was placed in a water bath at 55°C and reacted in a constant temperature water bath for 5h. After the reaction was completed, the mixture was filtered, evaporated in a rotary evaporator, and purified by column chromatography (petroleum ether / ethyl acetate = 5:1) to obtain a functional additive.
[0037] Example 3
[0038] 71 g of styrene-butadiene-acrylonitrile copolymer, 1.2 g of hindered phenol light stabilizer 770, 4 g of the functional additive prepared in Example 1, and 3 g of polyethylene wax were added to a high-speed mixer at 1000 r / min and stirred thoroughly for 15 minutes to obtain a mixture. The mixture was added to a twin-screw extruder, melt blended, extruded into granules, and dried in an oven at 80°C for 12 hours to obtain a thermoplastic resin composition.
[0039] Example 4
[0040] 78 g of styrene-butadiene-acrylonitrile copolymer, 1.5 g of hindered phenol light stabilizer 770, 8 g of the functional additive prepared in Example 2, and 5 g of EVA wax were added to a high-speed mixer at 1200 r / min and stirred thoroughly for 30 minutes to obtain a mixture. The mixture was added to a twin-screw extruder, melt blended, extruded into granules, and dried in an oven at 90°C for 24 hours to obtain a thermoplastic resin composition.
[0041] Example 5
[0042] 85 g of styrene-butadiene-acrylonitrile copolymer, 1.8 g of hindered phenol light stabilizer 770, 12 g of the functional additive prepared in Example 2, and 6 g of oleamide were added to a high-speed mixer at 1500 r / min and stirred thoroughly for 30 minutes to obtain a mixture. The mixture was added to a twin-screw extruder, melt blended, extruded into pellets, and dried in an oven at 100° C. for 24 hours to obtain a thermoplastic resin composition.
[0043] Comparative Example 1
[0044] The functional auxiliary agent in Example 5 was replaced by a hindered phenol antioxidant of the same mass, and the remaining steps were the same as those in Example 5 to prepare a thermoplastic resin composition.
[0045] Comparative Example 2
[0046] Commercially available ABS resin was used.
[0047] Examples 3, 4, 5 and Comparative Examples 1 and 2 were made into corresponding test shapes according to different standards and subjected to the following performance tests:
[0048] The tensile properties were determined using the national standard GB / T 1040.2-2006 “Determination of tensile properties of plastics Part 2: Test conditions for molded and extruded plastics”;
[0049] The limiting oxygen index was determined using the national standard GB / T 2406-2008 “Test method for combustion performance of plastics”;
[0050] The induction time of the sample was determined using the national standard GB / T 19466.6-2009 "Plastics Differential Scanning Calorimetry (DSC) Part 6: Determination of Oxidation Induction Time (Isothermal OIT) and Oxidation Induction Temperature (Dynamic OIT)";
[0051] The measured results are shown in the following table:
[0052] Test items Example 3 Example 4 Example 5 Comparative Example 1 Comparative Example 2 Tensile strength / MPa 42.2 41.9 41.7 42.3 43.9 Limiting oxygen index / % 26.7 27.2 27.7 18.9 19.5 Induction time / min 59 63 68 55 41
[0053] As can be seen from the above table, the thermoplastic resin composition prepared in the embodiment of the present invention has higher flame retardancy and antioxidant properties than the comparative example due to the addition of functional additives, and the functional additives have little effect on the mechanical properties of the embodiment. Therefore, the present invention has important application value in the field of automotive interior parts technology.
[0054] Throughout the specification, references to terms such as "one embodiment," "example," or "specific example" indicate that the specific features, structures, materials, or characteristics described in conjunction with that embodiment or example are included in at least one embodiment or example of the present invention. In this specification, schematic representations of these 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 any one or more embodiments or examples.
[0055] The above contents are merely examples and explanations of the present invention. Any modifications or additions made by those skilled in the art to the described specific embodiments, or replacements made in a similar manner, shall fall within the scope of protection of the present invention.
Claims
1. A thermoplastic resin composition, characterized in that Prepared by the following steps: Styrene-butadiene-acrylonitrile copolymer, light stabilizer, functional additives and processing aids are added to a high-speed mixer and fully stirred to obtain a mixture, which is then added to a twin-screw extruder for melt blending, extrusion granulation and drying to obtain a thermoplastic resin composition.
2. The thermoplastic resin composition according to claim 1, characterized in that The functional additive is prepared by the following steps: Step A1: Add thiodiethanol and diethylphosphinoacetic acid into a three-necked flask, then add toluene, stir at room temperature for 30-60 minutes, then add p-toluenesulfonic acid, heat the oil bath to 80°C, and react for 6-8 hours. The reaction is completed to obtain the first product; Step A2: Add the first product and β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionyl chloride to a three-necked flask, then add toluene, stir at room temperature for 15-20 minutes, then add triethylamine, and react in a water bath at 45-55°C for 3-5 hours. The reaction is completed to obtain a functional additive.
3. The thermoplastic resin composition according to claim 2, characterized in that In step A1, the ratio of thiodiethanol, diethylphosphinoacetic acid, toluene, and p-toluenesulfonic acid is 13.7 g:19.6 g:100 mL:0.8 g.
4. The thermoplastic resin composition according to claim 2, characterized in that In step A2, the ratio of the first product, β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionyl chloride, toluene, and triethylamine is 29.9 g:29.6 g:150 mL:10.1 g.
5. The thermoplastic resin composition according to claim 1, wherein The raw materials are calculated in parts by weight as follows: 71-85 parts of styrene-butadiene-acrylonitrile copolymer, 1.2-1.8 parts of light stabilizer, 4-12 parts of functional additives, and 3-6 parts of processing aids.
6. The thermoplastic resin composition according to claim 1, wherein The light stabilizer is a hindered phenol light stabilizer.
7. The thermoplastic resin composition according to claim 1, wherein The processing aid is one of polyethylene wax, EVA wax, oleamide and erucamide.
8. The thermoplastic resin composition according to claim 1, wherein The rotation speed of the high-speed mixer is 1000-1500 r / min, and the stirring time is 15-30 min.
9. The thermoplastic resin composition according to claim 1, wherein The drying condition is to dry in an oven at 80-100° C. for 12-24 hours.
10. Use of the thermoplastic resin composition according to claim 1 in the technical field of automotive interior parts.