Environment-friendly high-toughness flame-retardant ABS composition, preparation method and application thereof

Abstract

The application discloses an environment-friendly high-toughness flame-retardant ABS composition and a preparation method and application thereof, and mainly comprises the following raw materials in parts by weight: 2-3 parts of diantimony trioxide, 3-6 parts of brominated triazine, 1-3 parts of hexabromocyclododecane, 1-2 parts of HP-AHB type flame retardant, 80-85 parts of ABS resin composition, 0.1-0.5 parts of anti-dripping agent, 1-3 parts of zinc borate and 5-10 parts of nano calcium carbonate.The environment-friendly high-toughness flame-retardant ABS composition has the characteristics of high toughness and good flame-retardant effect, and the composite material has advantages, can be applied to the field of new energy vehicles, and has the advantages of low cost and high economic benefit, and has the value of being popularized.

Description

Technical Field

[0001] This invention relates to the field of flame retardant technology, specifically to an environmentally friendly, high-toughness flame-retardant ABS composition, its preparation method, and its application. Background Technology

[0002] Acrylonitrile-butadiene-styrene copolymer (ABS) is a terpolymer composed of acrylonitrile, butadiene, and styrene. It possesses excellent impact resistance, heat resistance, low-temperature resistance, chemical resistance, and electrical properties. It is also easy to process, has dimensional stability, and a good surface gloss. It is easy to paint and color, and can undergo secondary processing such as surface metallization, electroplating, welding, hot pressing, and bonding. It is widely used in industries such as machinery, automobiles, electronics, instrumentation, textiles, and construction, making it a highly versatile thermoplastic.

[0003] ABS resin possesses excellent mechanical properties, including high tensile strength, high tensile modulus, good toughness, and excellent abrasion resistance. However, ABS resin has an oxygen index of only 18-20%, classifying it as flammable. Therefore, improving the flame-retardant properties of ABS resin materials is of great significance.

[0004] Currently, bromine-antimony flame retardants are commonly used in the ABS plastic market due to their good flame retardant effect and minimal degradation of material properties. Antimony trioxide (Sb₂O₃) is a white powder with a melting point of 654℃, and is generally used in combination with bromine-based flame retardants to achieve a combined flame retardant effect. However, Sb₂O₃ is expensive and its price is rising year by year, leading to a continuous increase in the cost of flame-retardant ABS raw materials. Therefore, the development and application research of efficient, environmentally friendly, and low-cost flame retardants is particularly important.

[0005] The core component of new energy vehicles is the power battery system, and the system of vehicle power battery is generally made of synthetic materials such as functional plastics, which places higher demands on the flame retardant performance and mechanical properties of the materials.

[0006] Therefore, developing an environmentally friendly, high-toughness, flame-retardant ABS composition with low Sb2O3 content, good flame retardant properties, and excellent mechanical properties that can meet the application requirements of new energy vehicles is a technical problem that needs to be solved at this stage. Summary of the Invention

[0007] In view of this, the present invention provides an environmentally friendly high-toughness flame-retardant ABS composition, its preparation method and application. The environmentally friendly high-toughness flame-retardant ABS composition obtained by this application has low cost, good flame-retardant effect and good mechanical properties, and can be applied in the field of new energy vehicles.

[0008] To solve the above problems, the present invention adopts the following technical solution:

[0009] An environmentally friendly, high-toughness, flame-retardant ABS composition, its preparation method, and its application, wherein the method includes the following steps:

[0010] An environmentally friendly, high-toughness, flame-retardant ABS composition, wherein the environmentally friendly, high-toughness, flame-retardant ABS composition is mainly composed of the following raw materials in parts by weight: 2-3 parts antimony trioxide, 3-6 parts bromotriazine, 1-3 parts hexabromocyclododecane, 1-2 parts HP-AHB type flame retardant, 80-85 parts ABS resin composition, 0.1-0.5 parts anti-dripping agent, 1-3 parts zinc borate, and 5-10 parts nano calcium carbonate.

[0011] Furthermore, the environmentally friendly, high-toughness, flame-retardant ABS composition is mainly composed of the following raw materials in parts by weight: 2.5 parts antimony trioxide, 5 parts bromotriazine, 2 parts hexabromocyclododecane, 1.5 parts HP-AHB type flame retardant, 83 parts ABS resin composition, 0.3 parts anti-dripping agent, 2 parts zinc borate, and 7 parts nano calcium carbonate.

[0012] Furthermore, the HP-AHB type flame retardant is obtained by the following method: triethanolamine and ferrous acetate are mixed in a mass ratio of 2-3:1, and then heated to 65-75°C under stirring. Then, calcium hydrogen phosphate, magnesium hydrogen phosphate, and zinc phosphate are added, and the mixture is heated to 80-85°C under stirring and kept at that temperature for 3-5 hours to obtain the HP-AHB type flame retardant.

[0013] Furthermore, the mass ratio of the calcium hydrogen phosphate, magnesium hydrogen phosphate, and zinc phosphate is 2-4:2:1.

[0014] Furthermore, the ABS resin composition is obtained by mixing SAN resin and high-polymer powder in a mass ratio of 60-65:35-40.

[0015] Furthermore, the ABS resin composition is obtained by mixing SAN resin and high-polymer powder in a mass ratio of 65:35.

[0016] Furthermore, the average particle size of the SAN resin is 200-300 nm, and the average particle size of the high-polymer powder is 100-150 nm.

[0017] This application also provides a method for preparing the above-mentioned environmentally friendly, high-toughness, flame-retardant ABS composition, the method comprising the following steps: mixing antimony trioxide, tribromotriazine, hexabromocyclododecane, HP-AHB type flame retardant, ABS resin composition, anti-dripping agent, zinc borate and nano calcium carbonate evenly, granulating using an extruder, and making plastic samples using an injection molding machine to obtain the environmentally friendly, high-toughness, flame-retardant ABS composition.

[0018] The composite material of this application has the characteristics of high toughness and good flame retardancy, and can be applied in the field of new energy vehicles.

[0019] Compared with the prior art, the present invention has the following advantages:

[0020] 1. This invention provides an environmentally friendly, high-toughness, flame-retardant ABS composition. By adding flame-retardant components and reinforcing components to an ABS resin composition, the resulting ABS composition exhibits excellent flame-retardant properties and mechanical properties, and can be applied in the field of new energy vehicles.

[0021] 2. This invention addresses the problem of ABS's extreme flammability and low limiting oxygen index by compounding bromine-based flame retardants and antimony trioxide to improve flame retardancy. However, antimony trioxide is costly and difficult to obtain. The applicant further developed an HP-AHB type flame retardant that can partially replace antimony trioxide. Adding HP-AHB type flame retardant to the system allows it to exert flame retardant effects in both the gas phase and condensed phase. When the polymer burns, it decomposes to release PO·, which exerts a flame retardant effect in the gas phase and generates phosphorus-containing low-activity substances, promoting the formation of a dense char layer in the condensed phase, thus achieving flame retardancy in the condensed phase. Furthermore, it has a good synergistic flame retardant effect with bromine-antimony flame retardants, which can partially replace antimony trioxide, thereby reducing the amount of antimony trioxide used in the system and reducing costs while maintaining flame retardant performance. In addition, the applicant unexpectedly discovered that using the HP-AHB type flame retardant prepared in this application to replace part of the antimony trioxide results in environmentally friendly, high-toughness, flame-retardant ABS compositions with better mechanical properties.

[0022] 3. The ABS resin composition of the present invention is obtained by mixing SAN resin and high-polymer powder in a mass ratio of 65:35. Both SAN resin and high-polymer powder are in powder form with small particle size. In the experiment, it was found that mixing SAN resin and high-polymer powder in the above ratio to obtain the ABS resin composition can enhance the mixing effect between raw materials, thereby improving the quality of the finished product. Attached Figure Description

[0023] Figure 1 The image shows an electron microscope image of the material in the eighth group of the experimental examples;

[0024] Figure 2 This is an electron microscope image of the flame-retardant ABS composition obtained in Example 2. Detailed Implementation

[0025] The following embodiments can help those skilled in the art to more fully understand the present invention, but should not be construed as limiting the present invention in any way.

[0026] Example 1

[0027] This embodiment provides an environmentally friendly, high-toughness, flame-retardant ABS composition, which is mainly composed of the following raw materials in parts by weight: 2 parts antimony trioxide, 3 parts bromotriazine, 1 part hexabromocyclododecane, 1 part HP-AHB type flame retardant, 80 parts ABS resin composition, 0.1 parts anti-dripping agent, 1 part zinc borate, and 5 parts nano calcium carbonate.

[0028] The HP-AHB type flame retardant is obtained by the following method: triethanolamine and ferrous acetate are mixed in a mass ratio of 2:1, then heated to 65°C under stirring. Next, dicalcium phosphate, magnesium phosphate, and zinc phosphate are added in a mass ratio of 2:2:1, and the mixture is heated to 80°C under stirring and held at this temperature for 3 hours to obtain the HP-AHB type flame retardant. The ABS resin composition is obtained by mixing SAN resin and high-polymer powder in a mass ratio of 60:45. The average particle size of the SAN resin is 200 nm, and the average particle size of the high-polymer powder is 100 nm.

[0029] The method for preparing the above-mentioned environmentally friendly, high-toughness, flame-retardant ABS composition is as follows: according to the above-mentioned parts by weight, antimony trioxide, bromotriazine, hexabromocyclododecane, HP-AHB type flame retardant, ABS resin composition, anti-dripping agent, zinc borate and nano calcium carbonate are mixed evenly, granulated using an extruder, and plastic samples are made using an injection molding machine to obtain the environmentally friendly, high-toughness, flame-retardant ABS composition.

[0030] Example 2

[0031] This embodiment provides an environmentally friendly, high-toughness, flame-retardant ABS composition, which is mainly composed of the following raw materials in parts by weight: 2.5 parts antimony trioxide, 5 parts bromotriazine, 2 parts hexabromocyclododecane, 1.5 parts HP-AHB type flame retardant, 83 parts ABS resin composition, 0.3 parts anti-dripping agent, 2 parts zinc borate, and 7 parts nano calcium carbonate.

[0032] The HP-AHB type flame retardant is obtained by the following method: triethanolamine and ferrous acetate are mixed in a mass ratio of 2:1, then heated to 70°C under stirring. Next, dicalcium phosphate, magnesium phosphate, and zinc phosphate are added in a mass ratio of 3:2:1, and the mixture is heated to 82°C under stirring and held at this temperature for 4 hours to obtain the HP-AHB type flame retardant. The ABS resin composition is obtained by mixing SAN resin and high-polymer powder in a mass ratio of 65:35. The average particle size of the SAN resin is 250 nm, and the average particle size of the high-polymer powder is 120 nm.

[0033] The method for preparing the above-mentioned environmentally friendly, high-toughness, flame-retardant ABS composition is as follows: according to the above-mentioned parts by weight, antimony trioxide, bromotriazine, hexabromocyclododecane, HP-AHB type flame retardant, ABS resin composition, anti-dripping agent, zinc borate and nano calcium carbonate are mixed evenly, granulated using an extruder, and plastic samples are made using an injection molding machine to obtain the environmentally friendly, high-toughness, flame-retardant ABS composition.

[0034] Example 3

[0035] This embodiment provides an environmentally friendly, high-toughness, flame-retardant ABS composition, which is mainly composed of the following raw materials in parts by weight: 3 parts antimony trioxide, 6 parts bromotriazine, 3 parts hexabromocyclododecane, 2 parts HP-AHB type flame retardant, 85 parts ABS resin composition, 0.5 parts anti-dripping agent, 3 parts zinc borate, and 10 parts nano calcium carbonate.

[0036] The HP-AHB type flame retardant is obtained by the following method: triethanolamine and ferrous acetate are mixed in a mass ratio of 3:1, then heated to 75°C under stirring. Next, calcium hydrogen phosphate, magnesium hydrogen phosphate, and zinc phosphate are added in a mass ratio of 4:2:1, and the mixture is heated to 85°C under stirring and held at this temperature for 5 hours to obtain the HP-AHB type flame retardant. The ABS resin composition is obtained by mixing SAN resin and high-polymer powder in a mass ratio of 62:38. The average particle size of the SAN resin is 300 nm, and the average particle size of the high-polymer powder is 150 nm.

[0037] The method for preparing the above-mentioned environmentally friendly, high-toughness, flame-retardant ABS composition is as follows: according to the above-mentioned parts by weight, antimony trioxide, bromotriazine, hexabromocyclododecane, HP-AHB type flame retardant, ABS resin composition, anti-dripping agent, zinc borate and nano calcium carbonate are mixed evenly, granulated using an extruder, and plastic samples are made using an injection molding machine to obtain the environmentally friendly, high-toughness, flame-retardant ABS composition.

[0038] Experimental example:

[0039] To illustrate the effectiveness of this application, the applicant conducted group tests on the flame retardant effect and mechanical properties of products in each group, as follows:

[0040] Group 1: The environmentally friendly, high-toughness, flame-retardant ABS composition prepared by the method described in Example 2 of this application;

[0041] Group 2: Remove HP-AHB type flame retardant, use 4 parts of antimony trioxide, and follow the same procedure as Group 1.

[0042] Group 3: Remove HP-AHB flame retardant, otherwise the same as Group 1;

[0043] Group 4: The average particle size of the SAN resin and high-adhesion powder constituting the ABS resin composition is 6 mm, and other aspects are the same as Group 1;

[0044] Group 5: The mass ratio of SAN resin to high-polymer powder is 85:15, and other methods are the same as Group 1;

[0045] Group 6: The mass ratio of SAN resin to high-polymer powder is 45:55, and other methods are the same as Group 1;

[0046] Group 7: Environmentally friendly high-toughness flame-retardant ABS composition is mainly composed of the following raw materials in parts by weight: 1.5 parts antimony trioxide, 5 parts bromotriazine, 2 parts hexabromocyclododecane, 2.0 parts HP-AHB type flame retardant, 83 parts ABS resin composition, 0.3 parts anti-dripping agent, 2 parts zinc borate and 7 parts nano calcium carbonate, and other methods are the same as Group 1;

[0047] Group 8: Control group: ABS resin composition, all of which consist of SAN resin and high-polymer powder.

[0048] First, the vertical burning ratings of the above groups were compared. The vertical burning rating test was conducted according to GB / T 2408-2021 standard, using a horizontal vertical burning tester to test the samples. The sample dimensions were 125mm × 13mm × 2.5mm. During the test, the sample was ignited 10mm from the bottom and held for 10 seconds before being removed. After the sample extinguished, it was ignited again for 10 seconds. If the extinguishing time after both ignitions was less than 10 seconds and no molten droplets ignited the cotton ball, it passed the V-0 rating; if the extinguishing time after both ignitions was less than 30 seconds and no molten droplets ignited the cotton ball, it passed the V-1 rating; if the extinguishing time after both ignitions was less than 30 seconds and burning particles or droplets ignited the cotton ball, it passed the V-2 rating. Otherwise, exceeding the specified time or the flame burning to the fixture resulted in no burning rating.

[0049] The criteria for determining the vertical combustion rating are shown in Table 1:

[0050] Table 1 Vertical Combustion Rating and Criteria

[0051]

[0052] The vertical combustion rating and some mechanical properties of the products in each group were compared, and the results are shown in Table 2:

[0053] Table 2 Quality Comparison of Products in Each Group

[0054]

[0055] According to the results in Table 2, the HP-AHB type flame retardant of this application can replace part of the antimony trioxide, thereby improving the economic benefits of the product. In addition, after replacing antimony trioxide with the HP-AHB type flame retardant prepared by the method of this application, the mechanical properties of the product are improved. Furthermore, the experiment shows that the composition and morphology of the raw materials in the ABS resin composition also have a great influence on the quality of the product.

[0056] Electron micrographs of the products in the first and eighth groups are shown below. Figure 2 and Figure 1 As shown in the figure, Figure 1 In the middle, the ABS carbon layer is relatively loose and incomplete, with a large number of loose pores, loose structure, and discontinuity. This kind of incomplete carbon layer can hardly play any protective role for ABS material and basically cannot play the role of condensed phase flame retardant.

[0057] Figure 2 The char layer is dense and continuous, with no visible pores or cracks, enhancing both its continuity and integrity. This dense and complete char layer provides excellent insulation, strongly blocking heat and oxygen, preventing the transfer of combustion heat to the inner layer, and making it difficult for surrounding materials to heat up. It also isolates combustible volatiles, preventing them from providing fuel for the flame, thus acting as a flame retardant in the condensed phase. In summary, the formation of a dense and continuous char layer on the surface of the flame-retardant material is due to the introduction of HP-AHB, which significantly improves the charring ability of ABS, forming a denser char layer. This layer acts as a barrier against heat flow and gas transport, reducing the outward diffusion of volatile combustible gases, and blocking oxygen and heat exchange, thus providing flame retardancy in the condensed phase.

[0058] In summary, the environmentally friendly, high-toughness, flame-retardant ABS composition prepared by the method of this application has both good flame-retardant properties and excellent mechanical properties, and can be applied in the field of new energy vehicles.

[0059] The above description is a detailed description of the preferred embodiments of the present invention. However, the embodiments are not intended to limit the scope of the patent application of the present invention. All equivalent changes or modifications made under the technical spirit of the present invention should fall within the patent scope covered by the present invention.

Claims

1. An environmentally friendly high toughness flame retardant ABS composition, characterized in that, The environment-friendly high-toughness flame-retardant ABS composition is mainly composed of the following raw materials in parts by weight: 2-3 parts of antimony trioxide, 3-6 parts of brominated triazine, 1-3 parts of hexabromocyclododecane, 1-2 parts of HP-AHB type flame retardant, 80-85 parts of ABS resin composition, 0.1-0.5 parts of anti-dripping agent, 1-3 parts of zinc borate and 5-10 parts of nano calcium carbonate; The HP-AHB type flame retardant is obtained by mixing triethanolamine and ferrous acetate in a mass ratio of 2-3:1, then heating to 65-75 DEG C under stirring, then adding calcium hydrogen phosphate, magnesium hydrogen phosphate and zinc phosphate, continuing to heat to 80-85 DEG C under stirring, and keeping for 3-5 hours to obtain the HP-AHB type flame retardant; the mass ratio of calcium hydrogen phosphate, magnesium hydrogen phosphate and zinc phosphate is 2-4:2:1; The ABS resin composition is obtained by mixing SAN resin and high glue powder in a mass ratio of 60-65:35-40; the average particle size of the SAN resin is 200-300 nm, and the average particle size of the high glue powder is 100-150 nm.

2. The environmentally friendly high toughness flame retardant ABS composition according to claim 1, characterized in that, The environment-friendly high-toughness flame-retardant ABS composition is mainly composed of the following raw materials in parts by weight: 2.5 parts of antimony trioxide, 5 parts of brominated triazine, 2 parts of hexabromocyclododecane, 1.5 parts of HP-AHB type flame retardant, 83 parts of ABS resin composition, 0.3 parts of anti-dripping agent, 2 parts of zinc borate and 7 parts of nano calcium carbonate.

3. The environmentally friendly high toughness flame retardant ABS composition according to claim 1, characterized in that, The ABS resin composition is obtained by mixing SAN resin and high glue powder in a mass ratio of 65:

35.

4. A process for the preparation of an environmentally friendly high toughness flame retardant ABS composition according to any one of claims 1 to 3, characterized in that, The method comprises the following steps: uniformly mixing antimony trioxide, brominated triazine, hexabromocyclododecane, HP-AHB type flame retardant, ABS resin composition, anti-dripping agent, zinc borate and nano calcium carbonate, using an extruder to granulate, and using an injection molding machine to make plastic samples to obtain the environment-friendly high-toughness flame-retardant ABS composition.

5. Application of the ABS composition prepared by the method of claim 4 to new energy vehicles.

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