A flame-retardant ABS composite material and its preparation method

Abstract

This invention discloses a flame-retardant ABS composite material and its preparation method, belonging to the field of modified composite materials. The flame-retardant ABS composite material provided by this invention comprises the following components in parts by weight: 62-75 parts ABS resin, 12-25 parts halogenated flame retardant, 2-8 parts surface-modified sodium borate, 0.5-5 parts aminophenyl silicone oil-modified carbonate, and 1-14 parts additives. This invention mainly prepares the flame-retardant ABS composite material through mechanisms such as condensed phase flame retardancy, gas dilution, endothermic cooling, increasing thermal decomposition temperature, and inhibiting free radical chain reactions. It is environmentally friendly, antimony-free, exhibits excellent flame retardancy, good thermal stability, and good rigidity and toughness, possessing significant potential for widespread application.

Description

Technical Field

[0001] This invention belongs to the field of modified composite materials, specifically relating to a flame-retardant ABS composite material and its preparation method. Background Technology

[0002] ABS resin is a copolymer of styrene, butadiene, and acrylonitrile. ABS resin contains a polybutadiene phase with good toughness and impact strength. However, due to the presence of substituted tertiary carbon atoms in the polybutadiene phase, ABS resin is highly flammable, as oxygen readily abstracts hydrogen from butadiene, initiating oxidation. Ordinary ABS resin cannot achieve fire resistance and requires flame retardant modification.

[0003] Using ABS resin as the matrix, a certain amount and ratio of brominated flame retardants and antimony-containing compound flame retardant synergists can be added to prepare flame-retardant ABS with different vertical burning ratings. For example, Chinese patent CN 102391608 uses 10-25% of environmentally friendly brominated flame retardants (decabromodiphenyl ethane and brominated epoxy resin, used alone or in combination in a certain proportion) and 2-8% of flame retardant synergists (compound flame retardant synergists containing antimony compounds) to prepare flame-retardant ABS with a vertical burning rating of 1.6-3.0mm and UL94 V-0 level. Chinese patent CN119350796A discloses a 5VA high flame-retardant ABS resin composition and its preparation method, using aromatic brominated flame retardants, antimony-based flame retardant synergies (the antimony-based flame retardant synergies are selected from antimony trioxide, antimony pentoxide, or sodium antimonate), chlorinated polyethylene, and other components to prepare a high flame-retardant ABS resin composition. Chinese patent CN108148338A uses 8-10% environmentally friendly brominated flame retardant decabromodiphenyl ethane and 2-3 parts antimony trioxide to prepare flame-retardant ABS material with a vertical burning rating of V-0. Currently, the flame-retardant systems used in commercially available flame-retardant ABS are mainly based on bromo-antimony synergy systems. The bromine in bromo-antimony synergy systems mainly comes from common brominated flame retardants such as tetrabromobisphenol A, bromotriazine, decabromodiphenyl ethane, and brominated polystyrene; the antimony mainly comes from antimony-containing compound flame retardant synergies such as antimony oxides and antimonates. Among antimony-containing flame retardant synergies, antimony trioxide is the most commonly used. However, in recent years, with increasing public concern for environmental protection and ecological safety, relevant laws and regulations have been gradually improved. Studies have found that antimony trioxide is a Group B carcinogen and was considered for inclusion in the EU's RoHS restricted substance list in 2018, currently in the consultation phase. Given the risk of antimony trioxide being completely restricted and banned, the development of a flame-retardant system that completely eliminates the use of antimony trioxide is urgently needed. Summary of the Invention

[0004] To address the shortcomings of existing technologies, the present invention aims to provide a flame-retardant ABS composite material and its preparation method. The flame-retardant ABS composite material provided by the present invention can achieve good flame-retardant effects without containing antimony trioxide.

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

[0006] A flame-retardant ABS composite material, comprising the following components in parts by weight:

[0007] The composition includes 62-75 parts ABS resin, 12-25 parts halogenated flame retardant, 2-8 parts surface-modified sodium borate, 0.5-5 parts aminophenyl silicone oil-modified carbonate, and 1-14 parts additives; wherein:

[0008] The preparation method of aminophenyl silicone oil modified carbonate is as follows:

[0009] After cleaning and removing impurities, the carbonate is dispersed in a solvent and ultrasonically dispersed. Aminophenyl silicone oil is added, and ultrasonic dispersion continues. Finally, the solvent is removed to obtain the modified carbonate. Preferably, the carbonate is at least one of magnesium carbonate, aluminum carbonate, and strontium carbonate, with a particle size in the nanometer range; the solvent is an aqueous ethanol solution; the mass ratio of aminophenyl silicone oil to carbonate is (3-12):50; and the aminophenyl silicone oil is at least one of aminopropyl polydiphenylsiloxane and aminopropyl polymethylphenylsiloxane.

[0010] The preparation method of surface-modified sodium borate is as follows: sodium borate and a surface modifier are added to a dispersant, heated under reflux with stirring, and finally the dispersant is removed to obtain surface-modified sodium borate; the surface modifier includes a phosphate ester. Preferably, the surface modifier also includes a siloxane, and the mass ratio of phosphate ester, siloxane, and sodium borate is (0.3-8):(0-5):10. More preferably, the phosphate ester is hydroquinone bis(diphenyl phosphate), the siloxane is 1,3-di(chloromethyl)-1,1,3,3-tetramethyldisiloxane, and the sodium borate is anhydrous sodium borate or sodium borate octahydrate.

[0011] As a preferred technical solution, the additives include 0-5 parts of high-rubber powder, 0-8 parts of chlorinated polyethylene grafted acrylonitrile, 0.1-0.3 parts of antioxidant, and 0.2-0.7 parts of lubricant. Because the addition of large amounts of flame retardants, minerals, and other components reduces the toughness of the composite material, it easily causes product cracking and shortens its service life. Adding appropriate amounts of high-rubber powder and chlorinated polyethylene grafted acrylonitrile can improve the toughness of the material. Antioxidants can improve the material's resistance to heat and oxygen aging, and lubricants can improve the material's processing performance. More preferably, the antioxidant is at least one of antioxidant 168 and antioxidant 1076; the lubricant is at least one of calcium stearate and polytetrafluoroethylene; the chlorine content of the chlorinated polyethylene grafted acrylonitrile is 25-50%, and the AN content is 20-40%. In this invention, the chlorinated polyethylene grafted acrylonitrile utilizes halogenated chlorine to enhance the flame retardancy of the material, and the ethylene segment has good flexibility and toughness, which can improve the toughness of the material. The addition of acrylonitrile can improve the chemical resistance of the material.

[0012] As a preferred technical solution, the halogenated flame retardant is a chlorine-based flame retardant or a bromine-based flame retardant; specifically, one or more of the bromine-based flame retardants such as decabromodiphenyl ethane, bromotriazine, or brominated ethylene oxide can be selected.

[0013] This invention also provides a method for preparing the flame-retardant ABS composite material described above, comprising the following steps:

[0014] ABS resin, flame retardant, surface-modified sodium borate, aminophenyl silicone oil-modified carbonate, and additives are weighed according to the specified ratio and mixed evenly to obtain a mixture. This mixture is then melt-blended and extruded to granulate, yielding a flame-retardant ABS composite material. The preparation method of this invention is simple and suitable for mass industrial production.

[0015] Compared with the prior art, the present invention has the following beneficial effects:

[0016] This invention utilizes surface-modified sodium borate calcite. Firstly, the sodium borate calcite decomposes at high temperatures, losing its water of crystallization, thus absorbing heat to cool combustibles and dilute the oxygen concentration in the air. Secondly, at high temperatures, the sodium borate calcite decomposes to produce a B₂O₃ solid glass layer, which covers the surface of the combustible material, preventing the escape of flammable gases and further oxidative degradation. Sodium borate calcite can react with halogenated flame retardants upon heating to generate high-boiling-point solid coatings such as CaBr₂, NaBr, CaCl₂, and NaCl, further preventing the escape of flammable gases and oxidative degradation. Secondly, the BX₃ (where X is a halogen) produced by the combustion of sodium borate calcite and halogenated flame retardants reacts with gaseous water vapor to produce HX. HX in the flame can generate halogen atoms that effectively inhibit chain reactions between free radicals, suppressing chain transmission between free radicals and thus providing flame retardancy. Phosphate esters used for surface modification of sodium borate can promote carbonization at high temperatures, forming a carbon layer. This carbon layer acts as insulation and oxygen barrier, thereby inhibiting material degradation and combustion. Furthermore, phosphate esters can capture free radicals generated during combustion, thus interrupting the combustion reaction. At high temperatures, phosphate esters can degrade to produce phosphoric acid, which can further react with internal strontium carbonate to generate carbon dioxide, slowing down the combustion rate and decomposing the generated gases. This results in a porous, fluffy carbon layer on the surface, blocking the transmission of oxygen and flammable gases. In addition, this invention adds siloxanes to the surface modification of sodium borate. The siloxanes coated on the surface of sodium borate can form silica at high temperatures. This inorganic substance further enhances the stability of the carbon layer and improves its flame-retardant effect. Surface coating of sodium borate improves its dispersibility in resin and enhances interfacial bonding.

[0017] The flame-retardant ABS composite material provided by this invention also contains aminophenyl silicone oil-modified carbonate. The role of carbonate in this component is analyzed as follows: On the one hand, adding carbonate can improve the rigidity of the material; on the other hand, the large specific surface area of ​​nanoparticles can thicken the material, improve melt strength, and prevent the rapid diffusion of combustible materials. Taking strontium carbonate as an example, strontium carbonate will endothermally decompose at high temperatures, which can reduce the surface temperature of combustible materials. Furthermore, the carbon dioxide it generates can dilute the oxygen concentration in the air. In addition, carbon dioxide remains near the surface of the combustible material for a long time, covering the surface and reducing the combustion rate. Secondly, the gases produced by decomposition can form a porous, fluffy carbon layer on the material surface, blocking the transmission of oxygen and combustible gases. Furthermore, since chlorinated polyethylene grafted with acrylonitrile and halogenated flame retardants in the composite material will produce some weakly acidic substances in high-temperature environments, which will promote material degradation and lead to performance decline, the alkaline carbonate can neutralize these acidic substances, thereby improving the material performance.

[0018] The principle of modifying carbonates with aminophenyl silicone oil in this invention is analyzed as follows: (1) Modification with aminophenyl silicone oil can improve the dispersibility of nano-carbonates, reduce agglomeration, and reduce the impact on the strength of the substrate; (2) It decomposes at high combustion temperature, releases gas, reduces oxygen concentration, and plays a flame-retardant role; (3) Amino acids are prone to thermal reactions, causing cross-linking of siloxanes and resins, increasing the thermal decomposition temperature of the material, thereby improving the oxygen index and flame retardancy of the material; (4) Phenyl can combine with compounds containing nitrogen, phosphorus, halogens, etc., to form polymers with flame-retardant functions. These polymers can form a dense char layer during combustion, isolating oxygen and heat, thereby inhibiting the spread of flames. In addition, the conjugated structure in phenyl can also absorb the heat generated during combustion, reduce the combustion temperature of the material, and further improve the flame-retardant performance.

[0019] This invention mainly produces flame-retardant ABS composite materials through mechanisms such as condensed phase flame retardancy, gas dilution, heat absorption and cooling, increasing thermal decomposition temperature, and inhibiting free radical chain reaction. These materials are environmentally friendly and antimony-free, exhibit excellent flame retardancy, good thermal stability, and good rigidity and toughness, making them highly valuable for widespread application. Attached Figure Description

[0020] Figure 1 The results are the performance test results of the flame-retardant ABS composite materials prepared in Examples 1-13 and Comparative Examples 1-7; Figure 1 A plus sign indicates good thermal stability, while a minus sign indicates poor thermal stability. Detailed Implementation

[0021] The technical solutions in the embodiments of the present invention will be clearly and completely described below. 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 skilled in the art without creative effort are within the scope of protection of the present invention.

[0022] A flame-retardant ABS composite material comprises the following raw materials in parts by weight: 62-75 parts ABS resin, 12-25 parts halogenated flame retardant, 2-8 parts surface-modified sodium borate, 0.5-5 parts aminophenyl silicone oil-modified carbonate, and 1-14 parts additives; the additives include high-rubber powder, chlorinated polyethylene grafted acrylonitrile, antioxidants, and lubricants.

[0023] The ABS used is Tianjin Dagu DG-417, the halogenated flame retardant is commercially available bromine-based flame retardant - bromotriazine SR245, the chlorinated polyethylene grafted acrylonitrile is commercially available Xinnoco AN-g-CPE-30, the high-adhesion powder is commercially available Kumho Petrochemical HR-181, the sodium borate is commercially available sodium borate octahydrate, and the carbonate is commercially available nano-strontium carbonate with a specific surface area of ​​25-50 m². 2 / kg, particle size 50-110nm, resorcinol bis(diphenyl phosphate) (RDP) and 1,3-di(chloromethyl)-1,1,3,3-tetramethyldisiloxane are both commercially available, aminophenyl silicone oil is aminopropyl polydiphenylsiloxane, antioxidant 168 / antioxidant 1076 / calcium stearate / polytetrafluoroethylene and other processing aids are all commercially available.

[0024] In the examples and comparative examples, the samples were prepared by the following method, including the following steps:

[0025] ABS resin, halogenated flame retardant, high-rubber powder, chlorinated polyethylene grafted acrylonitrile, surface-modified sodium borate, aminophenyl silicone oil modified carbonate, antioxidant, and lubricant are mixed evenly and then added to a twin-screw extruder. After melt blending and extrusion granulation, flame-retardant ABS composite material is obtained. The temperatures of each extrusion zone in the twin-screw extruder are 180℃, 200℃, 210℃, 210℃, 210℃, 200℃, 190℃, 190℃, 190℃, and 210℃, respectively. The screw speed is 650 r / min, the vacuum negative pressure is 0.09 MPa, and the length-to-diameter ratio of the twin-screw extruder is 40:1.

[0026] Example 1

[0027] A flame-retardant ABS composite material comprises the following raw materials in parts by weight: 68 parts ABS resin, 5 parts high-rubber powder, 5 parts chlorinated polyethylene grafted acrylonitrile, 12 parts flame retardant, 6 parts surface-modified sodium borate, 3 parts aminophenyl silicone oil modified carbonate, 0.2 parts 168 antioxidant, 0.1 parts 1076 antioxidant, 0.5 parts calcium stearate, and 0.2 parts polytetrafluoroethylene.

[0028] The preparation method of surface-modified sodium borate is as follows: RDP, sodium borate, and 1,3-di(chloromethyl)-1,1,3,3-tetramethyldisiloxane are heated under reflux at 138°C for 3 hours while stirring in xylene. Finally, xylene is removed by distillation to obtain surface-modified sodium borate. The mass ratio of RDP, 1,3-di(chloromethyl)-1,1,3,3-tetramethyldisiloxane, and sodium borate is 1.6:1.4:10.

[0029] The preparation method of aminophenyl silicone oil modified carbonate is as follows: 50 parts of nano-strontium carbonate are washed and filtered four times in deionized water to remove impurities and metal ion residues, and to avoid degradation and chain scission of polymer materials during high-temperature processing, thereby reducing flame retardant performance. Then, the impurity-removed nano-strontium carbonate is dispersed in an ethanol aqueous solution (ethanol:water = 78:22), ultrasonically dispersed, and then 6 parts of aminophenyl silicone oil are added. After ultrasonic dispersion again, the mixture is centrifuged and dried to obtain aminophenyl silicone oil modified carbonate.

[0030] Example 2

[0031] A flame-retardant ABS composite material comprises the following raw materials in parts by weight: 64 parts ABS resin, 5 parts high-rubber powder, 5 parts chlorinated polyethylene grafted acrylonitrile, 16 parts flame retardant, 6 parts surface-modified sodium borate, 3 parts aminophenyl silicone oil modified carbonate, 0.2 parts 168 antioxidant, 0.1 parts 1076 antioxidant, 0.5 parts calcium stearate, and 0.2 parts polytetrafluoroethylene.

[0032] The preparation methods for surface-modified sodium borate and aminophenyl silicone oil-modified carbonates are the same as in Example 1.

[0033] Example 3

[0034] A flame-retardant ABS composite material comprises the following raw materials in parts by weight: 55 parts ABS resin, 5 parts high-rubber powder, 5 parts chlorinated polyethylene grafted acrylonitrile, 25 parts flame retardant, 6 parts surface-modified sodium borate, 3 parts aminophenyl silicone oil modified carbonate, 0.2 parts 168 antioxidant, 0.1 parts 1076 antioxidant, 0.5 parts calcium stearate, and 0.2 parts polytetrafluoroethylene.

[0035] The preparation methods for surface-modified sodium borate and aminophenyl silicone oil-modified carbonates are the same as in Example 1.

[0036] Example 4

[0037] A flame-retardant ABS composite material comprises the following raw materials in parts by weight: 68 parts ABS resin, 5 parts high-rubber powder, 5 parts chlorinated polyethylene grafted acrylonitrile, 16 parts flame retardant, 2 parts surface-modified sodium borate, 3 parts aminophenyl silicone oil modified carbonate, 0.2 parts 168 antioxidant, 0.1 parts 1076 antioxidant, 0.5 parts calcium stearate, and 0.2 parts polytetrafluoroethylene.

[0038] The preparation methods for surface-modified sodium borate and aminophenyl silicone oil-modified carbonates are the same as in Example 1.

[0039] Example 5

[0040] A flame-retardant ABS composite material comprises the following raw materials in parts by weight: 62 parts ABS resin, 5 parts high-rubber powder, 5 parts chlorinated polyethylene grafted acrylonitrile, 16 parts flame retardant, 8 parts surface-modified sodium borate, 3 parts aminophenyl silicone oil modified carbonate, 0.2 parts 168 antioxidant, 0.1 parts 1076 antioxidant, 0.5 parts calcium stearate, and 0.2 parts polytetrafluoroethylene.

[0041] The preparation methods for surface-modified sodium borate and aminophenyl silicone oil-modified carbonates are the same as in Example 1.

[0042] Example 6

[0043] A flame-retardant ABS composite material comprises the following raw materials in parts by weight: 64 parts ABS resin, 5 parts high-rubber powder, 5 parts chlorinated polyethylene grafted acrylonitrile, 16 parts flame retardant, 6 parts surface-modified sodium borate, 3 parts aminophenyl silicone oil modified carbonate, 0.2 parts 168 antioxidant, 0.1 parts 1076 antioxidant, 0.5 parts calcium stearate, and 0.2 parts polytetrafluoroethylene.

[0044] The preparation method of surface-modified sodium borate is the same as in Example 1.

[0045] The preparation method of modified nano-strontium carbonate as aminophenyl silicone oil modified carbonate is the same as that in Example 1, except that the amount of aminophenyl silicone oil is adjusted to 3 parts. All other processes are the same as in Example 1.

[0046] Example 7

[0047] A flame-retardant ABS composite material comprises the following raw materials in parts by weight: 65 parts ABS resin, 5 parts high-rubber powder, 5 parts chlorinated polyethylene grafted acrylonitrile, 16 parts flame retardant, 6 parts surface-modified sodium borate, 3 parts aminophenyl silicone oil modified carbonate, 0.2 parts 168 antioxidant, 0.1 parts 1076 antioxidant, 0.5 parts calcium stearate, and 0.2 parts polytetrafluoroethylene.

[0048] The preparation method of surface-modified sodium borate is the same as in Example 1.

[0049] The preparation method of aminophenyl silicone oil modified carbonate is the same as that in Example 1, except that the amount of aminophenyl silicone oil is adjusted to 12 parts. All other processes are the same as in Example 1.

[0050] Example 8

[0051] A flame-retardant ABS composite material comprises the following raw materials in parts by weight: 65 parts ABS resin, 5 parts high-rubber powder, 5 parts chlorinated polyethylene grafted acrylonitrile, 16 parts flame retardant, 6 parts surface-modified sodium borate, 3 parts aminophenyl silicone oil modified carbonate, 0.2 parts 168 antioxidant, 0.1 parts 1076 antioxidant, 0.5 parts calcium stearate, and 0.2 parts polytetrafluoroethylene.

[0052] The preparation method of aminophenyl silicone oil modified carbonate is the same as in Example 1.

[0053] The preparation method of surface-modified sodium borate is the same as that in Example 1, except that the mass ratio of RDP, 1,3-di(chloromethyl)-1,1,3,3-tetramethyldisiloxane and sodium borate is 0.5:1.75:10. All other processes are the same as in Example 1.

[0054] Example 9

[0055] A flame-retardant ABS composite material comprises the following raw materials in parts by weight: 65 parts ABS resin, 5 parts high-rubber powder, 5 parts chlorinated polyethylene grafted acrylonitrile, 16 parts flame retardant, 6 parts surface-modified sodium borate, 3 parts aminophenyl silicone oil modified carbonate, 0.2 parts 168 antioxidant, 0.1 parts 1076 antioxidant, 0.5 parts calcium stearate, and 0.2 parts polytetrafluoroethylene.

[0056] The preparation method of aminophenyl silicone oil modified carbonate is the same as in Example 1.

[0057] The preparation method of surface-modified sodium borate is the same as that in Example 1, except that the mass ratio of RDP, 1,3-di(chloromethyl)-1,1,3,3-tetramethyldisiloxane and sodium borate is 3:1.75:10. All other processes are the same as in Example 1.

[0058] Example 10

[0059] A flame-retardant ABS composite material comprises the following raw materials in parts by weight: 65 parts ABS resin, 5 parts high-rubber powder, 5 parts chlorinated polyethylene grafted acrylonitrile, 16 parts flame retardant, 6 parts surface-modified sodium borate, 3 parts aminophenyl silicone oil modified carbonate, 0.2 parts 168 antioxidant, 0.1 parts 1076 antioxidant, 0.5 parts calcium stearate, and 0.2 parts polytetrafluoroethylene.

[0060] The preparation method of aminophenyl silicone oil modified carbonate is the same as in Example 1.

[0061] The preparation method of surface-modified sodium borate is as follows: RDP and sodium borate are heated under reflux at 138°C for 3 hours while stirring in p-xylene, and then the p-xylene is removed by distillation to obtain surface-modified sodium borate; wherein the mass ratio of RDP to sodium borate is 1.6:10.

[0062] Example 11

[0063] A flame-retardant ABS composite material comprises the following raw materials in parts by weight: 65 parts ABS resin, 5 parts high-rubber powder, 5 parts chlorinated polyethylene grafted acrylonitrile, 16 parts flame retardant, 6 parts surface-modified sodium borate, 3 parts aminophenyl silicone oil modified carbonate, 0.2 parts 168 antioxidant, 0.1 parts 1076 antioxidant, 0.5 parts calcium stearate, and 0.2 parts polytetrafluoroethylene.

[0064] The preparation method of aminophenyl silicone oil modified carbonate is the same as in Example 1.

[0065] The preparation method of surface-modified sodium borate is as follows: RDP, sodium borate, and 1,3-di(chloromethyl)-1,1,3,3-tetramethyldisiloxane are heated under reflux at 138°C for 3 hours with stirring, and the xylene is removed by distillation to obtain surface-modified sodium borate. The mass ratio of RDP, 1,3-di(chloromethyl)-1,1,3,3-tetramethyldisiloxane, and sodium borate is 1.6:3:10.

[0066] Example 12

[0067] A flame-retardant ABS composite material comprises the following raw materials in parts by weight: 69 parts ABS resin, 5 parts high-rubber powder, 16 parts flame retardant, 6 parts surface-modified sodium borate, 3 parts aminophenyl silicone oil modified carbonate, 0.2 parts 168 antioxidant, 0.1 parts 1076 antioxidant, 0.5 parts calcium stearate, and 0.2 parts polytetrafluoroethylene.

[0068] The preparation methods for surface-modified sodium borate and aminophenyl silicone oil-modified carbonates are the same as in Example 1.

[0069] Example 13

[0070] A flame-retardant ABS composite material comprises the following raw materials in parts by weight: 61 parts ABS resin, 5 parts high-rubber powder, 8 parts chlorinated polyethylene grafted acrylonitrile, 16 parts flame retardant, 6 parts surface-modified sodium borate, 3 parts aminophenyl silicone oil modified carbonate, 0.2 parts 168 antioxidant, 0.1 parts 1076 antioxidant, 0.5 parts calcium stearate, and 0.2 parts polytetrafluoroethylene.

[0071] The preparation methods for surface-modified sodium borate and aminophenyl silicone oil-modified carbonates are the same as in Example 1.

[0072] Comparative Example 1

[0073] A flame-retardant ABS composite material comprises the following raw materials in parts by weight: 73 parts ABS resin, 5 parts high-rubber powder, 5 parts chlorinated polyethylene grafted acrylonitrile, 16 parts flame retardant, 0.2 parts 168 antioxidant, 0.1 parts 1076 antioxidant, 0.5 parts calcium stearate, and 0.2 parts polytetrafluoroethylene.

[0074] Comparative Example 2

[0075] A flame-retardant ABS composite material comprises the following raw materials in parts by weight: 67 parts ABS resin, 5 parts high-rubber powder, 5 parts chlorinated polyethylene grafted acrylonitrile, 16 parts flame retardant, 6 parts surface-modified sodium borate, 0.2 parts 168 antioxidant, 0.1 parts 1076 antioxidant, 0.5 parts calcium stearate, and 0.2 parts polytetrafluoroethylene.

[0076] The preparation method of modified sodium borate is the same as in Example 1.

[0077] Comparative Example 3

[0078] A flame-retardant ABS composite material comprises the following raw materials in parts by weight: 70 parts ABS resin, 5 parts high-rubber powder, 5 parts chlorinated polyethylene grafted acrylonitrile, 16 parts flame retardant, 3 parts aminophenyl silicone oil modified carbonate, 0.2 parts 168 antioxidant, 0.1 parts 1076 antioxidant, 0.5 parts calcium stearate, and 0.2 parts polytetrafluoroethylene.

[0079] The preparation method of aminophenyl silicone oil modified carbonate is the same as in Example 1.

[0080] Comparative Example 4

[0081] A flame-retardant ABS composite material comprises the following raw materials in parts by weight: 80 parts ABS resin, 5 parts high-rubber powder, 5 parts chlorinated polyethylene grafted acrylonitrile, 6 parts surface-modified sodium borate, 3 parts aminophenyl silicone oil modified carbonate, 0.2 parts 168 antioxidant, 0.1 parts 1076 antioxidant, 0.5 parts calcium stearate, and 0.2 parts polytetrafluoroethylene.

[0082] The preparation methods for surface-modified sodium borate and aminophenyl silicone oil-modified carbonates are the same as in Example 1.

[0083] Comparative Example 5

[0084] A flame-retardant ABS composite material comprises the following raw materials in parts by weight: 69 parts ABS resin, 5 parts chlorinated polyethylene grafted acrylonitrile, 16 parts flame retardant, 6 parts surface-modified sodium borate, 3 parts aminophenyl silicone oil modified carbonate, 0.2 parts 168 antioxidant, 0.1 parts 1076 antioxidant, 0.5 parts calcium stearate, and 0.2 parts polytetrafluoroethylene.

[0085] The preparation methods for surface-modified sodium borate and aminophenyl silicone oil-modified carbonates are the same as in Example 1.

[0086] Comparative Example 6

[0087] A flame-retardant ABS composite material comprises the following raw materials in parts by weight: 64 parts ABS resin, 5 parts high-rubber powder, 5 parts chlorinated polyethylene grafted acrylonitrile, 16 parts flame retardant, 6 parts sodium borate, 3 parts aminophenyl silicone oil modified carbonate, 0.2 parts 168 antioxidant, 0.1 parts 1076 antioxidant, 0.5 parts calcium stearate, and 0.2 parts polytetrafluoroethylene.

[0088] The preparation method of aminophenyl silicone oil modified carbonate is the same as in Example 1.

[0089] Comparative Example 7

[0090] A flame-retardant ABS composite material comprises the following raw materials in parts by weight: 64 parts ABS resin, 5 parts high-rubber powder, 5 parts chlorinated polyethylene grafted acrylonitrile, 16 parts flame retardant, 6 parts surface-modified sodium borate, 3 parts nano-strontium carbonate, 0.2 parts 168 antioxidant, 0.1 parts 1076 antioxidant, 0.5 parts calcium stearate, and 0.2 parts polytetrafluoroethylene.

[0091] The preparation method of surface-modified sodium borate is the same as in Example 1.

[0092] The properties of the flame-retardant ABS composite materials prepared in Examples 1-13 and Comparative Examples 1-5 of this invention were tested. The test items and standards were as follows: tensile strength, ASTM D638; drop weight impact energy test: ASTM D5420; flame retardancy test: UL-94, flame retardancy rating and burning time; chemical resistance test: ESCR, tensile specimens coated with glacial acetic acid, and fracture time was tested; the test results are as follows. Figure 1 As shown.

[0093] from Figure 1 As can be seen, by adding flame retardants, high-polymer powder, chlorinated polyethylene grafted acrylonitrile, modified sodium borate, and aminophenyl silicone oil modified carbonate, the material exhibits excellent chemical resistance, flame retardancy, toughness, strength, and thermal stability. Example 2 demonstrates the best overall performance, indicating that its addition ratio and powder modification method are superior to others.

[0094] By comparing Comparative Example 1 and Example 2, it can be seen that without the addition of surface-modified sodium borate and aminophenyl silicone oil-modified carbonate, the flame retardancy, thermal stability and chemical resistance of the material are significantly reduced.

[0095] By comparing Comparative Example 2 with Example 2, it can be seen that without the addition of aminophenyl silicone oil modified carbonate, the flame retardancy, thermal stability and chemical resistance of the material are slightly reduced.

[0096] By comparing Comparative Example 3 with Example 2, it can be seen that without the addition of surface-modified sodium borate, the flame retardancy and thermal stability of the material are greatly reduced.

[0097] By comparing Comparative Example 4 with Example 2, it can be seen that without the addition of bromine-based flame retardants, the material loses its flame retardant properties.

[0098] By comparing Comparative Example 5 and Example 2, it can be seen that without the addition of high-polymer powder, the flame retardancy of the material is improved, but its toughness is greatly reduced.

[0099] By comparing Example 1 with Comparative Example 6, it can be seen that the performance of sodium borate is greatly reduced without modification, especially its flame retardant properties and toughness.

[0100] By comparing Example 1 with Comparative Example 7, it can be seen that the performance of nano-strontium carbonate is greatly reduced without modification, especially its flame retardancy and toughness.

[0101] In the description of this specification, references to terms such as "an embodiment," "example," "specific example," etc., indicate that a specific feature, structure, material, or characteristic described in connection with that embodiment or example is included in at least one embodiment or example of the invention. In this specification, illustrative expressions of the above terms do not necessarily refer to the same embodiment or example. Furthermore, the specific features, structures, materials, or characteristics described may be combined in any suitable manner in one or more embodiments or examples.

[0102] The foregoing has shown and described the basic principles, main features, and advantages of the present invention. Those skilled in the art should understand that the present invention is not limited to the above embodiments. The embodiments and descriptions in the specification are merely illustrative of the principles of the invention. Various changes and modifications can be made to the invention without departing from its spirit and scope, and all such changes and modifications fall within the scope of the claimed invention.

Claims

1. A flame-retardant ABS composite material, characterized in that: The components include the following parts by weight: The composition includes 62-75 parts ABS resin, 12-25 parts halogenated flame retardant, 2-8 parts surface-modified sodium borate, 0.5-5 parts aminophenyl silicone oil-modified carbonate, and 1-14 parts additives. The preparation method of the surface-modified sodium borate is as follows: sodium borate and a surface modifier are added to a dispersant, heated under reflux with stirring, and finally the dispersant is removed to obtain surface-modified sodium borate; the surface modifier includes a phosphate ester; the phosphate ester is resorcinol bis(diphenyl phosphate). The additives include 1-5 parts of high-rubber powder, 5-8 parts of chlorinated polyethylene grafted acrylonitrile, 0.1-0.3 parts of antioxidant, and 0.2-0.7 parts of lubricant.

2. The flame-retardant ABS composite material according to claim 1, characterized in that: The preparation method of the aminophenyl silicone oil modified carbonate is as follows: After cleaning and removing impurities, the carbonate is dispersed in a solvent and ultrasonically dispersed. After adding aminophenyl silicone oil, ultrasonic dispersion is continued. Finally, the solvent is removed to obtain the modified carbonate.

3. The flame-retardant ABS composite material according to claim 2, characterized in that: The mass ratio of the aminophenyl silicone oil to the carbonate is (3-12):50; the aminophenyl silicone oil is at least one of aminopropyl polydiphenylsiloxane and aminopropyl polymethylphenylsiloxane.

4. The flame-retardant ABS composite material according to claim 1, characterized in that: The surface modifier also includes siloxane, and the mass ratio of the phosphate ester, siloxane, and sodium borate is (0.3-8):(0-5):

10.

5. The flame-retardant ABS composite material according to claim 4, characterized in that: The phosphate ester is hydroquinone bis(diphenyl phosphate ester), and the siloxane is 1,3-di(chloromethyl)-1,1,3,3-tetramethyldisiloxane.

6. The flame-retardant ABS composite material according to any one of claims 1 to 5, characterized in that: The carbonate is at least one of magnesium carbonate, aluminum carbonate, and strontium carbonate.

7. The flame-retardant ABS composite material according to claim 6, characterized in that: The antioxidant is at least one of antioxidant 168 and antioxidant 1076; the lubricant is at least one of calcium stearate and polytetrafluoroethylene.

8. The method for preparing the flame-retardant ABS composite material according to any one of claims 1 to 7, characterized in that: Includes the following steps: Weigh out ABS resin, flame retardant, surface-modified sodium borate, aminophenyl silicone oil-modified carbonate, and additives according to the formula, mix them evenly to obtain a mixture, and then melt-blend and extrude granulate the mixture to obtain a flame-retardant ABS composite material.

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