High-glowing-wire high-limit-oxygen-index flame-retardant ABS material, preparation method and application thereof

Abstract

This invention belongs to the field of polymer materials technology, and specifically relates to a high glow wire and high limiting oxygen index flame-retardant ABS material, its preparation method, and its application. The flame-retardant ABS material comprises the following raw materials in the indicated mass percentages: 55%–80% ABS resin, 5%–16% brominated flame retardant, 2%–6% synergistic flame retardant, 2%–10% magnesium salt whiskers, 4%–10% water-washed montmorillonite, and processing aids; the synergistic flame retardant includes zinc stannate. The flame-retardant ABS material of this invention exhibits high glow wire and high limiting oxygen index.

Description

Technical Field

[0001] This invention belongs to the field of polymer materials technology, and specifically relates to a high glow wire, high limiting oxygen index flame-retardant ABS material, its preparation method and application. Background Technology

[0002] Acrylonitrile-butadiene-styrene (ABS) resin is a high-strength, tough, and easily processed thermoplastic polymer material, widely used in electronics, home appliances, automobiles, construction, and consumer goods. ABS is an excellent insulating material, and its electrical properties do not change significantly with temperature and humidity.

[0003] The limiting oxygen index is a method for evaluating the relative flammability of plastics and other polymer materials. It is very effective in determining how easily a material burns when it comes into contact with a flame in air, and therefore has received attention from countries around the world.

[0004] Like most organic polymer materials, ABS resin is flammable, with a low limiting oxygen index (LOI) (18.3%–18.8%). Generally, an OX of <22% is considered flammable, 22%–27% is considered combustible, and >27% is considered flame-retardant. ABS burns rapidly and releases large amounts of toxic gases and black smoke, posing a significant threat to human safety and the environment, thus hindering practical applications. Currently, the LIO of conventional flame-retardant ABS materials on the market is between 24% and 27%, which still does not meet the requirements for some products with high flame-retardant standards.

[0005] Meanwhile, the commonly used flame-retardant system for flame-retardant ABS on the market is a compound system of brominated flame retardants and antimony trioxide, with a glow wire ignition temperature of generally 700-750℃, which is difficult to meet the requirements. Therefore, improving the glow wire ignition temperature of flame-retardant ABS is of great significance and is currently a key focus of flame-retardant ABS research and development. Summary of the Invention

[0006] This invention aims to at least solve one of the technical problems existing in the prior art. To this end, this invention proposes a flame-retardant ABS material with high glow wire density and high limiting oxygen index. Furthermore, this invention also proposes a method for preparing this flame-retardant ABS material and its applications.

[0007] Specifically, the present invention adopts the following technical solution:

[0008] The first aspect of the present invention is to provide a flame-retardant ABS material, said flame-retardant ABS material comprising the following raw materials in the indicated mass percentages:

[0009] ABS resin 55%–80%

[0010] Bromine-based flame retardants: 5%–16%

[0011] Synergistic flame retardant 2%–6%

[0012] Magnesium salt whiskers 2%–10%

[0013] Water-washed montmorillonite 4%–10%

[0014] Processing aids;

[0015] The synergistic flame retardant includes zinc stannate.

[0016] Compared to existing technologies, this invention uses zinc stannate as a synergistic flame retardant, replacing the traditional antimony trioxide synergistic flame retardant. This increases the glow wire temperature of the flame-retardant ABS material and avoids the influence of antimony on the glow wire performance. Simultaneously, magnesium salt whiskers and water-washed montmorillonite are added to the flame-retardant ABS material. The magnesium salt whiskers undergo a dehydration reaction during combustion, absorbing a large amount of external heat and thus lowering the temperature of the matrix material. Furthermore, the water vapor generated during dehydration dilutes the temperature of the gases in the flame zone, significantly increasing the glow wire ignition temperature of the flame-retardant ABS material. Water-washed montmorillonite has a large interlayer spacing and a large specific surface area, exhibiting good dispersibility in the flame-retardant ABS material. This results in better interfacial compatibility between the ABS resin polymer and montmorillonite, playing a synergistic flame-retardant role and improving the limiting oxygen index. Therefore, through the combined action of zinc stannate, magnesium salt whiskers, and water-washed montmorillonite, the flame-retardant ABS material of this invention possesses a high glow wire temperature and a high limiting oxygen index.

[0017] In some embodiments of the present invention, the flame-retardant ABS material comprises raw materials with the following mass content:

[0018] ABS resin 55.5%–76.5%

[0019] Brominated flame retardants 10%–16%

[0020] Synergistic flame retardant 3%–6%

[0021] Magnesium salt whiskers: 3%–8%

[0022] Water-washed montmorillonite 4%–8%

[0023] Processing aids: 3%–10%.

[0024] In some embodiments of the present invention, the flame-retardant ABS material comprises raw materials with the following mass content:

[0025] ABS resin 60%–75%

[0026] Brominated flame retardants 10%–15%

[0027] Synergistic flame retardant 3%–6%

[0028] Magnesium salt whiskers: 3%–8%

[0029] Water-washed montmorillonite 4%–8%

[0030] Processing aids: 3%–10%.

[0031] In some embodiments of the present invention, the flame-retardant ABS material comprises raw materials with the following mass content:

[0032] ABS resin 60%–70%

[0033] Brominated flame retardants 10%–15%

[0034] Synergistic flame retardant 3%–6%

[0035] Magnesium salt whiskers: 5%–8%

[0036] Water-washed montmorillonite 4%–8%

[0037] Processing aids: 3%–10%.

[0038] In some embodiments of the present invention, the ABS resin has a glue content of 10% to 20%, preferably 12% to 16%. Preferably, the ABS resin can be any one or more of Shanghai Gaoqiao Petrochemical's 8391, Tianjin Dagu's DG-417, etc.

[0039] In some embodiments of the present invention, the brominated flame retardant includes one or more of bromotriazine, tris(tribromophenyl)triazine, decabromodiphenyl ethane, and brominated polystyrene.

[0040] In some embodiments of the present invention, the magnesium salt whiskers comprise hydrated basic magnesium sulfate whiskers. Preferably, the diameter of the magnesium salt whiskers is 0.5–10 μm, more preferably 1–5 μm; and the length is 30–2500 μm, more preferably 50–2000 μm.

[0041] In some embodiments of the present invention, the D of the water-washed montmorillonite 50 ≤40μm, D is preferred 50 <40μm, more preferably 5-38μm; the average wafer thickness of the water-washed montmorillonite is less than 25nm; the average interlayer spacing of the water-washed montmorillonite is 0.2-0.6nm, preferably 0.3-0.5nm.

[0042] In some embodiments of the present invention, the processing aid includes any one or more of toughening agents, antioxidants, and lubricants, preferably a combination of toughening agents, antioxidants, and lubricants.

[0043] In some embodiments of the present invention, the toughening agent comprises any one or more of methyl methacrylate-butadiene-styrene terpolymer and high-polymer powder, preferably including high-polymer powder.

[0044] In some embodiments of the present invention, the antioxidant includes any one or more of hindered phenolic antioxidants and phosphite antioxidants, preferably a composition of hindered phenolic antioxidants and phosphite antioxidants. In the composition of hindered phenolic antioxidants and phosphite antioxidants, the mass ratio of the hindered phenolic antioxidant to the phosphite antioxidant is 1:0.5 to 2, preferably 1:0.8 to 1.2.

[0045] The hindered phenolic antioxidants and phosphite antioxidants can be selected from materials commonly used in the field, such as N,N'-1,6-hexylene-di-[3,5-di-tert-butyl-4-hydroxyphenylpropionamide] (antioxidant 1098), antioxidant 1010, antioxidant 1076, and antioxidant 1024; the phosphite antioxidants can be selected from (2,4-di-tert-butylphenyl) phosphite triester, triphenyl phosphite, and diphenyl isooctyl phosphite.

[0046] In some embodiments of the present invention, the lubricant comprises fatty amide lubricants, preferably ethylene bis-stearamide.

[0047] In some embodiments of the present invention, the toughening agent has a mass content of 0-6% in the flame-retardant ABS material, preferably 3%-6%.

[0048] In some embodiments of the present invention, the antioxidant content in the flame-retardant ABS material is 0-1% by mass, preferably 0.1%-0.5%.

[0049] In some embodiments of the present invention, the lubricant has a mass content of 0-1% in the flame-retardant ABS material, preferably 0.1%-0.5%.

[0050] In some embodiments of the present invention, the glow wire ignition temperature of the flame-retardant ABS material is ≥800°C (IEC60695-2-13, 1.5mm), and can reach 825°C or higher (IEC 60695-2-13, 1.5mm).

[0051] In some embodiments of the present invention, the glow wire ignition temperature of the flame-retardant ABS material is ≥825°C (IEC60695-2-13, 3.0mm), and can reach 850°C and above (IEC 60695-2-13, 3.0mm).

[0052] In some embodiments of the present invention, the flame-retardant ABS material achieves a flame-retardant rating of UL 94V0 (1.5mm, UL94).

[0053] In some embodiments of the present invention, the limiting oxygen index of the flame-retardant ABS material is >27% (ASTM D2863), and can reach 31% or higher (ASTM D2863).

[0054] A second aspect of the present invention is to provide a method for preparing the flame-retardant ABS material, comprising the following steps: mixing and melting various raw materials to obtain the flame-retardant ABS material.

[0055] More specifically, the raw materials are mixed, melt-extruded, and the flame-retardant ABS material is obtained.

[0056] In some embodiments of the present invention, the ABS resin in the raw material is dried before melting (or mixing), and the temperature of the dried material is 70-100°C, preferably 80-90°C; the drying time is 1-10 hours, preferably 2-8 hours.

[0057] In some embodiments of the present invention, the mixing time is 2 to 15 minutes, preferably 5 to 8 minutes.

[0058] In some embodiments of the present invention, the melt extrusion is carried out in a twin-screw extruder, wherein the processing temperature of each zone of the twin-screw extruder is 190–200°C and the screw speed is 250–300 r / min.

[0059] A third aspect of this invention is to provide the application of the flame-retardant ABS material in the manufacture of home appliances, automobiles, or electronic and electrical products. The flame-retardant ABS material of this invention has a high glow wire temperature and a high limiting oxygen index, which can meet the safety requirements of the home appliance, automotive, and electronic and electrical industries.

[0060] A fourth aspect of the present invention is to provide a method of applying the flame-retardant ABS material, comprising the step of injection molding the flame-retardant ABS material.

[0061] In some embodiments of the present invention, the injection molding process conditions are as follows: nozzle temperature 190-220°C, preferably 200-210°C; zone temperature 190-220°C, such as 200°C, 195°C, 190°C; holding time 2-4s; injection pressure 40-60MPa.

[0062] Compared with the prior art, the beneficial effects of the present invention are:

[0063] 1. This invention uses zinc stannate instead of traditional antimony trioxide as a synergistic flame retardant. On the one hand, it avoids the impact of antimony on the glow wire performance and improves the glow wire temperature of flame-retardant ABS material; on the other hand, it optimizes resource allocation in an environment where antimony resources are increasingly scarce.

[0064] 2. This invention introduces water-washed montmorillonite into flame-retardant ABS material. Through the principle of hydration, the interlayer spacing of montmorillonite is expanded, the specific surface area is increased, and the purity is improved, giving it good dispersion performance. This results in better interfacial compatibility between ABS resin polymer and montmorillonite, playing a synergistic flame-retardant role and thus improving the limiting oxygen index.

[0065] 3. When flame-retardant ABS materials made by adding magnesium salt whiskers are burned, the dehydration reaction of hydrated basic magnesium sulfate whiskers can absorb a large amount of external heat, thereby reducing the temperature of the matrix material. Moreover, the water vapor generated by dehydration can dilute the temperature of the gas in the flame zone, thereby significantly increasing the glow wire ignition temperature of the flame-retardant ABS material and improving the rigidity of the material to a certain extent.

[0066] 4. The synergistic effect of water-washed montmorillonite and magnesium salt whiskers allows the material to pass the 1.5mm-V0 test even with a small amount of addition, significantly improving the oxygen index and glow wire ignition temperature. At the same time, the material's rigidity is greatly improved while its toughness remains good, resulting in excellent overall performance and unexpected results.

[0067] 5. The preparation method of this invention is simple and the process is easy to implement. The flame-retardant ABS material obtained can meet the product safety requirements of the home appliance, automobile and electronic industries. Detailed Implementation

[0068] The technical solution of the present invention will be further illustrated below with reference to specific embodiments. Unless otherwise specified, the raw materials used in the following embodiments can be obtained from conventional commercial channels; unless otherwise specified, the processes employed are conventional processes in the art.

[0069] Examples 1 to 5 below each provide a flame-retardant ABS material, the raw material composition of which is shown in Table 1.

[0070] For comparison, Table 1 also provides Comparative Examples 1 to 5. The difference between Comparative Example 1 and Example 2 is that the raw materials do not contain washed montmorillonite and magnesium salt whiskers, and the content of brominated flame retardant and zinc stannate is increased to balance the raw materials. The difference between Comparative Example 2 and Example 2 is that zinc stannate is replaced with an equal mass of antimony trioxide. The difference between Comparative Example 3 and Example 5 is that the raw materials do not contain magnesium salt whiskers. The difference between Comparative Example 4 and Example 5 is that the raw materials do not contain washed montmorillonite. The difference between Comparative Example 5 and Example 1 (or Example 4) is that the content of washed montmorillonite is reduced.

[0071] The preparation methods of flame-retardant ABS materials in Examples 1-5 and Comparative Examples 1-5 are as follows: After drying each raw material at 80°C for 4 hours, it is added to a high-speed mixer. The mixer speed is adjusted to 500 r / min, and the mixture is stirred for 5 minutes. Then, it is transferred to a twin-screw extruder for extrusion, cooling, granulation, and drying to obtain the flame-retardant ABS material. The processing temperature of each zone of the twin-screw extruder is 190-200°C, and the screw speed is 300 r / min.

[0072] First, the flame-retardant ABS material was dried, and then injection molded (injection molding process conditions: nozzle temperature of 210℃, temperature of each zone of 210℃, 200℃, 190℃, holding time of 4s, injection pressure of 60MPa) as standard test specimens for performance testing. The test results are shown in Table 2.

[0073] Table 1. Raw material composition of flame-retardant ABS materials in Examples 1-5 and Comparative Examples 1-5

[0074]

[0075] Note:

[0076] ABS resin: DG-417, Tianjin Dagu;

[0077] Toughening agent: HR181, Kumho Chemical Co., Ltd., South Korea;

[0078] Brominated flame retardant: RDT-8, Shouguang Weidong;

[0079] Antimony trioxide: 99.5%, Sunstar;

[0080] Antioxidants: Irganox 1010 and Irganox 168, BASF; the mass ratio of Irganox 1010 to Irganox 168 is 1:1.

[0081] Table 2 Performance test data of flame-retardant ABS materials in Examples 1-5 and Comparative Examples 1-5

[0082]

[0083] Note:

[0084] Performance testing methods:

[0085] Tensile strength: tested according to ASTM D638 standard;

[0086] Bending strength: tested according to ASTM D790 standard;

[0087] Flexural modulus: tested according to ASTM D790 standard;

[0088] Notched impact strength: tested according to ASTM D256 standard;

[0089] Flame retardant performance: tested according to UL94 standard;

[0090] Glow wire ignition resistance (glow wire ignition temperature GWIT): Tested according to IEC 60695-2-13 standard;

[0091] Limiting oxygen index: Tested according to ASTM D2863 standard.

[0092] As can be seen from the test results of Example 2 and Comparative Example 2, although the flame-retardant ABS materials prepared using zinc stannate and antimony trioxide as synergistic flame retardants have similar mechanical properties and comparable flame-retardant properties, both achieving the UL94 1.5mm V0 rating, there are significant differences in their glow wire performance, especially for GWIT 1.5mm. With zinc stannate as a synergistic flame retardant, GWIT 1.5mm reaches a temperature as high as 825°C, significantly higher than the 775°C with antimony trioxide, requiring a higher temperature to ignite. Therefore, using zinc stannate as a synergistic flame retardant can effectively improve the glow wire flame resistance of flame-retardant ABS materials.

[0093] Meanwhile, as can be seen from Comparative Examples 1, 3, and 4 (compared with Examples 2 or 5), the introduction of magnesium salt whiskers effectively solved the problem of low ignition temperature of the glow wire in flame-retardant ABS material, and the rigidity (flexural strength, modulus) of the flame-retardant ABS material was significantly improved; the use of water-washed montmorillonite in the system had a certain synergistic effect on flame retardancy and improved the limiting oxygen index.

[0094] In summary, under the synergistic effect of zinc stannate, water-washed montmorillonite, and magnesium salt whiskers, the flame-retardant ABS materials prepared in Examples 1-5 can achieve a limiting oxygen index of over 27 and an ignition temperature of over 800°C with a 1.5mm glow wire. At the same time, the material rigidity is greatly improved, the toughness is good, and the overall performance is excellent, demonstrating unexpected results.

[0095] The above embodiments are preferred embodiments of the present invention, but the embodiments of the present invention are not limited to the above embodiments. Any changes, modifications, substitutions, combinations, or simplifications made without departing from the spirit and principle of the present invention shall be considered equivalent substitutions and shall be included within the protection scope of the present invention.

Claims

1. A flame-retardant ABS material, characterized in that: The flame-retardant ABS material comprises the following raw materials by mass content: ABS resin 55.5%~76.5% Brominated flame retardants 10%–16% Synergistic flame retardant 3%–6% Magnesium salt whiskers: 2%–8% Water-washed montmorillonite 4%–8% Processing aids 3%–10%; The synergistic flame retardant is zinc stannate; Based on the total mass of the flame-retardant ABS material, the processing aids include the following components in terms of mass content: toughening agent 3-6%, antioxidant 0.1-0.5%, and lubricant 0.1-0.5%.

2. The flame-retardant ABS material according to claim 1, characterized in that: The flame-retardant ABS material comprises the following raw materials by mass content: ABS resin 60%–75% Bromine-based flame retardants 10%–15% Synergistic flame retardant 3%–6% Magnesium salt whiskers: 3%–8% Water-washed montmorillonite 4%–8% Processing aids: 3%–10%.

3. The flame-retardant ABS material according to any one of claims 1 to 2, characterized in that: The ABS resin has a glue content of 10% to 20%.

4. The flame-retardant ABS material according to any one of claims 1 to 2, characterized in that: The bromine-based flame retardants include one or more of the following: bromotriazine, tris(tribromophenyl)triazine, decabromodiphenyl ethane, and brominated polystyrene.

5. The flame-retardant ABS material according to any one of claims 1 to 2, characterized in that: The magnesium salt whiskers include hydrated basic magnesium sulfate whiskers.

6. A method for preparing the flame-retardant ABS material according to any one of claims 1 to 5, characterized in that: The process includes the following steps: mixing and melting the raw materials to obtain the flame-retardant ABS material.

7. The use of the flame-retardant ABS material according to any one of claims 1 to 5 in the manufacture of household appliances, automobiles or electronic and electrical products.

8. The method of applying the flame-retardant ABS material according to any one of claims 1 to 5, characterized in that: This includes the step of injection molding the flame-retardant ABS material.

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