Environment-friendly ABS (Acrylonitrile Butadiene Styrene) composite material for recycled automotive trim and preparation method thereof

Abstract

The invention relates to the technical field of high polymer materials, in particular to an environment-friendly ABS (acrylonitrile-butadiene-styrene) composite material for recycled automotive trim and a preparation method of the environment-friendly ABS composite material. Comprising the following steps: mixing and stirring ABS resin, modified SBS resin, an antibacterial homopolymer, an antioxidant, an anti-dripping agent and a lubricant, and carrying out melt extrusion granulation at 200-250 DEG C through a twin-screw extruder to obtain the ABS composite material. The novel ABS composite material has the beneficial effects that the ABS resin, the antibacterial homopolymer and the modified SBS resin are subjected to melt extrusion together to obtain the novel ABS composite material, and the antibacterial and flame-retardant effects of the novel ABS composite material as the automotive trim are effectively improved.

Description

Technical Field

[0001] The invention relates to the technical field of polymer materials, in particular to an environmentally friendly ABS composite material for recycling and regenerating automobile interior decoration and a preparation method thereof. Background Art

[0002] The application of ABS plastic in automobile interiors is of great significance. Due to its good mechanical properties and processing properties, it is widely used in automobile parts, including interior parts such as cushions, interior panels, etc. However, with the increase in the number of cars, the number of scrapped cars is also rising, which has led to the generation of a large amount of waste ABS plastics. With the impact of plastic accumulation on the environment, some manufacturers have begun to turn their attention to the recycling and reuse of ABS plastics. The recycling of ABS plastics can not only reduce environmental pollution, but also effectively save resources and reduce energy consumption. Through correct classification and processing, ABS plastics can be remade into various products, such as new plastics, pipes and building materials. In addition, ABS plastics can also be recycled through technologies such as pyrolysis and gasification to extract valuable chemicals and fuels.

[0003] As far as car interiors are concerned, the recycling of ABS plastics is equally important, not only helping to reduce dependence on raw materials, but also reducing environmental load. Although some progress has been made in the recycling of ABS, it is still not safe enough for car interiors. For example, ABS itself does not have flame retardant properties. Under certain conditions, ABS materials will burn quickly and produce a lot of black smoke and toxic substances, posing safety hazards; in terms of antibacterial properties, the effect of adding antibacterial agents to achieve antibacterial properties is limited.

[0004] Therefore, the present invention prepares an environmentally friendly ABS composite material for recycled automobile interior decoration. Summary of the invention

[0005] The purpose of the present invention is to provide a method for preparing an environmentally friendly ABS composite material for recycled automobile interior decoration, so as to solve the problems raised in the above background technology.

[0006] In order to solve the above technical problems, the present invention provides the following technical solutions:

[0007] More optimally, the ABS composite material comprises the following components: by weight, 100-150 parts of ABS resin, 30-40 parts of modified SBS resin, 10-15 parts of antibacterial homopolymer, 1-2 parts of antioxidant, 1-2 parts of anti-dripping agent, and 1-2 parts of lubricant.

[0008] More optimally: the preparation process of the antibacterial homopolymer is:

[0009] Step 1: (1) Mix 3-phenyl-2-acryloyl chloride and toluene to obtain a 3-phenyl-2-acryloyl chloride solution; (2) Mix triethylamine, 6-bromohexanol and dichloromethane, add the 3-phenyl-2-acryloyl chloride solution dropwise at 0°C, and after the addition is complete, stir at room temperature overnight to obtain intermediate A; as shown in the following figure:

[0010] Step 2: Mix 2,2-dimethoxy-2-phenylacetophenone with intermediate A, irradiate with ultraviolet light for 1-2 hours, filter, wash the precipitate with tetrahydrofuran, and dry to obtain intermediate B; as shown in the following figure:

[0011] Step 3: Mix the intermediate B with N-ethyl-N-hydroxyethylaniline, heat to 60-70°C, react for 4-5 hours, cool to room temperature, add tetrahydrofuran, pour into petroleum ether, mix and stir, and separate to obtain the antibacterial homopolymer. As shown in the figure below:

[0012] More optimally, the intermediate A comprises the following components: by weight, 1-2 parts of triethylamine, 15-20 parts of 6-bromohexanol, 30-40 parts of dichloromethane, and 15-20 parts of 3-phenyl-2-acryloyl chloride solution.

[0013] More optimally, the intermediate B comprises the following components: 1-2 parts of 2,2-dimethoxy-2-phenylacetophenone and 10-15 parts of intermediate A by weight.

[0014] More optimally, the antibacterial homopolymer comprises the following components: by weight, 10-12 parts of intermediate B, 8-9 parts of N-ethyl-N-hydroxyethylaniline, 3-4 parts of tetrahydrofuran, and 30-40 parts of petroleum ether.

[0015] More optimally: the preparation process of the modified SBS resin is: DOPO (9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide), SBS resin (styrene-butadiene-styrene block copolymer), and 1,2-dichlorobenzene are mixed at 130° C., stirred for 2-4 hours, heated to 160-180° C., and reacted for 15-18 hours to obtain the modified SBS resin.

[0016] More optimally, the modified SBS resin comprises the following components: by weight, 130-140 parts of DOPO, 40-50 parts of SBS resin, and 75-80 parts of 1,2-dichlorobenzene.

[0017] More optimally: the antioxidant includes one or more of antioxidant 1010, antioxidant 1076, and antioxidant 1098; the anti-dripping agent is polytetrafluoroethylene; and the lubricant is calcium stearate.

[0018] More optimally: the process includes: mixing ABS resin, modified SBS resin, antibacterial homopolymer, antioxidant, anti-dripping agent and lubricant, and melt-extruding and granulating them at 200-250° C. through a twin-screw extruder to obtain an ABS composite material.

[0019] The present invention melt-extrudes ABS resin, antibacterial homopolymer and modified SBS resin together to obtain a new type of ABS composite material, which effectively improves its antibacterial and flame retardant effects as automobile interior decoration. The details are as follows:

[0020] First, the quaternary ammonium salt antibacterial substance synthesized by the present invention exists in the form of a homopolymer, which can maintain or enhance the antibacterial activity. Due to its appropriate carbon chain length, its compatibility with the matrix ABS resin is improved, and the homopolymer can reduce the migration and volatilization of the antibacterial agent from the small molecule form due to its high molecular weight and compatibility with the matrix, thereby achieving a more lasting antibacterial effect in plastic products. At the same time, the use of high molecular weight antibacterial homopolymers can reduce environmental pollution problems caused by the use of small molecule antibacterial agents, because small molecule antibacterial agents may accumulate in the environment and cause potential negative impacts on the ecosystem;

[0021] Second, the present invention modifies SBS resin with DOPO, wherein DOPO can react with double bonds in SBS resin to give SBS resin flame retardant properties. In addition, SBS resin and ABS resin have similar structures and good compatibility. Therefore, the flame retardant properties of the obtained ABS composite material are also improved. DETAILED DESCRIPTION

[0022] The preferred embodiments of the present invention are described below in conjunction with the accompanying drawings. It should be understood that the technical solutions in the embodiments of the present invention will be clearly and completely described below. Obviously, the described embodiments 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 creative work are within the scope of protection of the present invention.

[0023] It should be noted that there is no special restriction on the manufacturers of the raw materials involved in the present invention.

[0024] Embodiment 1: A method for preparing an environmentally friendly ABS composite material for recycled automobile interior, comprising the following steps:

[0025] Preparation of antibacterial homopolymer:

[0026] Step 1: (1) Mix 5 parts of 3-phenyl-2-acryloyl chloride and 30 parts of toluene to obtain a 3-phenyl-2-acryloyl chloride solution; (2) Mix 1 part of triethylamine, 15 parts of 6-bromohexanol and 30 parts of dichloromethane, and add 15 parts of the 3-phenyl-2-acryloyl chloride solution dropwise at 0°C. After the addition is complete, stir at room temperature overnight to obtain intermediate A;

[0027] Step 2: Mix 1 part of 2,2-dimethoxy-2-phenylacetophenone with 10 parts of intermediate A, irradiate with ultraviolet light for 1 hour, filter, wash the precipitate with tetrahydrofuran, and dry to obtain intermediate B;

[0028] Step 3: Mix 10 parts of intermediate B with 8 parts of N-ethyl-N-hydroxyethylaniline, heat to 60°C, react for 4 hours, cool to room temperature, add 3 parts of tetrahydrofuran, pour into 30 parts of petroleum ether, mix and stir, and separate to obtain an antibacterial homopolymer.

[0029] The preparation process of the modified SBS resin is as follows: 130 parts of DOPO, 40 parts of SBS resin, and 75 parts of 1,2-dichlorobenzene are mixed at 130° C., stirred for 2 hours, heated to 160° C., reacted for 15 hours, and obtained the modified SBS resin.

[0030] 100 parts of ABS resin, 30 parts of modified SBS resin, 10 parts of antibacterial homopolymer, 1 part of antioxidant 1010, 1 part of polytetrafluoroethylene and 1 part of calcium stearate were mixed and stirred, and melt-extruded and granulated at 200° C. through a twin-screw extruder to obtain an ABS composite material.

[0031] Embodiment 2: A method for preparing an environmentally friendly ABS composite material for recycled automobile interior, comprising the following steps:

[0032] Preparation of antibacterial homopolymer:

[0033] Step 1: (1) Mix 5 parts of 3-phenyl-2-acryloyl chloride and 30 parts of toluene to obtain a 3-phenyl-2-acryloyl chloride solution; (2) Mix 2 parts of triethylamine, 20 parts of 6-bromohexanol and 40 parts of dichloromethane, and add 20 parts of the 3-phenyl-2-acryloyl chloride solution dropwise at 0°C. After the addition is complete, stir at room temperature overnight to obtain intermediate A;

[0034] Step 2: Mix 2 parts of 2,2-dimethoxy-2-phenylacetophenone with 15 parts of intermediate A, irradiate with ultraviolet light for 1 hour, filter, wash the precipitate with tetrahydrofuran, and dry to obtain intermediate B;

[0035] Step 3: Mix 12 parts of intermediate B with 8 parts of N-ethyl-N-hydroxyethylaniline, heat to 60°C, react for 4 hours, cool to room temperature, add 4 parts of tetrahydrofuran, pour into 40 parts of petroleum ether, mix and stir, and separate to obtain an antibacterial homopolymer.

[0036] The preparation process of the modified SBS resin is as follows: 140 parts of DOPO, 50 parts of SBS resin, and 80 parts of 1,2-dichlorobenzene are mixed at 130° C., stirred for 2 hours, heated to 160° C., reacted for 15 hours, and obtained the modified SBS resin.

[0037] 150 parts of ABS resin, 40 parts of modified SBS resin, 15 parts of antibacterial homopolymer, 2 parts of antioxidant 1010, 2 parts of polytetrafluoroethylene and 2 parts of calcium stearate were mixed and stirred, and melt-extruded and granulated at 200° C. through a twin-screw extruder to obtain an ABS composite material.

[0038] Embodiment 3: A method for preparing an environmentally friendly ABS composite material for recycled automobile interior, comprising the following steps:

[0039] Preparation of antibacterial homopolymer:

[0040] Step 1: (1) Mix 5 parts of 3-phenyl-2-acryloyl chloride and 30 parts of toluene to obtain a 3-phenyl-2-acryloyl chloride solution; (2) Mix 1.5 parts of triethylamine, 18 parts of 6-bromohexanol and 35 parts of dichloromethane, and add 18 parts of the 3-phenyl-2-acryloyl chloride solution dropwise at 0°C. After the addition is complete, stir at room temperature overnight to obtain intermediate A;

[0041] Step 2: Mix 1.5 parts of 2,2-dimethoxy-2-phenylacetophenone with 18 parts of intermediate A, irradiate with ultraviolet light for 1 hour, filter, wash the precipitate with tetrahydrofuran, and dry to obtain intermediate B;

[0042] Step 3: Mix 11 parts of intermediate B with 8.5 parts of N-ethyl-N-hydroxyethylaniline, heat to 60°C, react for 4 hours, cool to room temperature, add 3.5 parts of tetrahydrofuran, pour into 35 parts of petroleum ether, mix and stir, and separate to obtain an antibacterial homopolymer.

[0043] The preparation process of the modified SBS resin is as follows: 135 parts of DOPO, 45 parts of SBS resin, and 78 parts of 1,2-dichlorobenzene are mixed at 130° C., stirred for 2 hours, heated to 160° C., reacted for 15 hours, and obtained the modified SBS resin.

[0044] 120 parts of ABS resin, 35 parts of modified SBS resin, 12 parts of antibacterial homopolymer, 1.5 parts of antioxidant 1010, 1.5 parts of polytetrafluoroethylene and 1.5 parts of calcium stearate were mixed and stirred, and melt-extruded and granulated at 200° C. through a twin-screw extruder to obtain an ABS composite material.

[0045] Comparative Example 1: No antibacterial homopolymer was added, and the rest was the same as Example 3, specifically as follows:

[0046] The preparation process of the modified SBS resin is as follows: 135 parts of DOPO, 45 parts of SBS resin, and 78 parts of 1,2-dichlorobenzene are mixed at 130° C., stirred for 2 hours, heated to 160° C., reacted for 15 hours, and obtained the modified SBS resin.

[0047] 120 parts of ABS resin, 35 parts of modified SBS resin, 1.5 parts of antioxidant 1010, 1.5 parts of polytetrafluoroethylene and 1.5 parts of calcium stearate were mixed and stirred, and melt-extruded and granulated at 200° C. through a twin-screw extruder to obtain an ABS composite material.

[0048] Comparative Example 2: No modified SBS resin was added, and the rest was the same as Example 3, specifically as follows:

[0049] Preparation of antibacterial homopolymer:

[0050] Step 1: (1) Mix 5 parts of 3-phenyl-2-acryloyl chloride and 30 parts of toluene to obtain a 3-phenyl-2-acryloyl chloride solution; (2) Mix 1.5 parts of triethylamine, 18 parts of 6-bromohexanol and 35 parts of dichloromethane, and add 18 parts of the 3-phenyl-2-acryloyl chloride solution dropwise at 0°C. After the addition is complete, stir at room temperature overnight to obtain intermediate A;

[0051] Step 2: Mix 1.5 parts of 2,2-dimethoxy-2-phenylacetophenone with 18 parts of intermediate A, irradiate with ultraviolet light for 1 hour, filter, wash the precipitate with tetrahydrofuran, and dry to obtain intermediate B;

[0052] Step 3: Mix 11 parts of intermediate B with 8.5 parts of N-ethyl-N-hydroxyethylaniline, heat to 60°C, react for 4 hours, cool to room temperature, add 3.5 parts of tetrahydrofuran, pour into 35 parts of petroleum ether, mix and stir, and separate to obtain an antibacterial homopolymer.

[0053] 120 parts of ABS resin, 12 parts of antibacterial homopolymer, 1.5 parts of antioxidant 1010, 1.5 parts of polytetrafluoroethylene and 1.5 parts of calcium stearate were mixed and stirred, and melt-extruded and granulated at 200° C. through a twin-screw extruder to obtain an ABS composite material.

[0054] Testing experiment: (1) The SBS composite materials obtained in Examples 1-3 and Comparative Examples 1-2 were tested for antibacterial effect according to QB / T2591 "Test method for antibacterial performance and antibacterial effect of antibacterial plastics", and the tested bacteria were Escherichia coli and Staphylococcus aureus; (2) The SBS composite materials obtained in Examples 1-3 and Comparative Examples 1-2 were tested for oxygen index according to the national standard GB / T 10707 "Determination of combustion performance of rubber". The obtained data are shown in the following table: project Example 1 Example 2 Example 3 Comparative Example 1 Comparative Example 2 Escherichia coli sterilization rate% 98.9 99.4 99.9 78.9 97.5 Staphylococcus aureus sterilization rate% 98.6 99.5 99.9 79.7 95.7 Oxygen Index 36 34 37 32 24

[0055] Conclusion: Examples 1-3 melt-extrude ABS resin, antibacterial homopolymer and modified SBS resin together to obtain a new type of ABS composite material, which effectively improves its antibacterial and flame retardant effects as automotive interior. Comparative Example 1 does not add antibacterial homopolymer, which reduces the antibacterial effect of the material; Comparative Example 2 does not add modified SBS resin, which reduces the flame retardant effect of the material.

[0056] Finally, it should be noted that the above description is only a preferred example of the present invention and is not intended to limit the present invention. Although the present invention has been described in detail with reference to the aforementioned embodiments, those skilled in the art can still modify the technical solutions described in the aforementioned embodiments or replace some of the technical features therein by equivalents. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention shall be included in the protection scope of the present invention.

Claims

1. A method for preparing an environmentally friendly ABS composite material for recycled automobile interior, characterized in that: The ABS composite material comprises the following components: by weight, 100-150 parts of ABS resin, 30-40 parts of modified SBS resin, 10-15 parts of antibacterial homopolymer, 1-2 parts of antioxidant, 1-2 parts of anti-dripping agent and 1-2 parts of lubricant.

2. The method for preparing a recycled and regenerated environmentally friendly ABS composite material for automobile interior decoration according to claim 1, characterized in that: The preparation process of the antibacterial homopolymer is as follows: Step 1: (1) Mix 3-phenyl-2-acryloyl chloride and toluene to obtain a 3-phenyl-2-acryloyl chloride solution; (2) Mix triethylamine, 6-bromohexanol and dichloromethane, add the 3-phenyl-2-acryloyl chloride solution dropwise at 0°C, and after the addition is complete, stir at room temperature overnight to obtain intermediate A; Step 2: Mix 2,2-dimethoxy-2-phenylacetophenone with intermediate A, irradiate with ultraviolet light for 1-2 hours, filter, wash the precipitate with tetrahydrofuran, and dry to obtain intermediate B; Step 3: Mix the intermediate B with N-ethyl-N-hydroxyethylaniline, heat to 60-70°C, react for 4-5 hours, cool to room temperature, add tetrahydrofuran, pour into petroleum ether, mix and stir, and separate to obtain the antibacterial homopolymer.

3. The method for preparing a recycled and regenerated environmentally friendly ABS composite material for automobile interior decoration according to claim 2, characterized in that: The intermediate A comprises the following components: by weight, 1-2 parts of triethylamine, 15-20 parts of 6-bromo-n-hexanol, 30-40 parts of dichloromethane, and 15-20 parts of 3-phenyl-2-acryloyl chloride solution.

4. The method for preparing a recycled and regenerated environmentally friendly ABS composite material for automobile interior decoration according to claim 2, characterized in that: The intermediate B comprises the following components: 1-2 parts of 2,2-dimethoxy-2-phenylacetophenone and 10-15 parts of intermediate A by weight.

5. The method for preparing a recycled and regenerated environmentally friendly ABS composite material for automobile interior decoration according to claim 2, characterized in that: The antibacterial homopolymer comprises the following components: by weight, 10-12 parts of intermediate B, 8-9 parts of N-ethyl-N-hydroxyethylaniline, 3-4 parts of tetrahydrofuran, and 30-40 parts of petroleum ether.

6. The method for preparing a recycled and regenerated environmentally friendly ABS composite material for automobile interior decoration according to claim 1, characterized in that: The preparation process of the modified SBS resin is as follows: DOPO (9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide), SBS resin (styrene-butadiene-styrene block copolymer), and 1,2-dichlorobenzene are mixed at 130° C., stirred for 2-4 hours, heated to 160-180° C., reacted for 15-18 hours, and obtained the modified SBS resin.

7. The method for preparing a recycled and regenerated environmentally friendly ABS composite material for automobile interior decoration according to claim 6, characterized in that: The modified SBS resin comprises the following components: by weight, 130-140 parts of DOPO, 40-50 parts of SBS resin, and 75-80 parts of 1,2-dichlorobenzene.

8. The method for preparing a recycled and regenerated environmentally friendly ABS composite material for automobile interior decoration according to claim 1, characterized in that: The antioxidant includes one or more of antioxidant 1010, antioxidant 1076, and antioxidant 1098; the anti-dripping agent is polytetrafluoroethylene; and the lubricant is calcium stearate.

9. A method for preparing an environmentally friendly ABS composite material for recycled automobile interior according to any one of claims 1 to 8, characterized in that: The process comprises the following steps: mixing ABS resin, modified SBS resin, antibacterial homopolymer, antioxidant, anti-dripping agent and lubricant, and then melting, extruding and granulating the mixture at 200-250° C. through a twin-screw extruder to obtain an ABS composite material.

Images