An ABS composition, its preparation method and application

Abstract

The present invention relates to an ABS composition, a preparation method and an application thereof. The components include: ABS, a brominated flame retardant, tris(3-nitrophenyl)phosphine, nano-tin dioxide-coated antimony trioxide, and carbon black. The present invention achieves a low emission effect, and the material is not prone to generate volatiles during hot processing and is not prone to generate appearance air filament defects.

Description

Technical Field

[0001] The present invention belongs to the field of modified plastics, and particularly relates to an ABS composition, a preparation method and an application thereof. Background Art

[0002] ABS resin, an acrylonitrile butadiene styrene terpolymer, is widely used in home appliances, energy, office equipment, security equipment, and electronic and electrical applications. However, ABS is not easily carbonized and has a relatively low oxygen index, requiring flame retardant modification to meet fire protection requirements.

[0003] Antimony white, a micron-sized, high-whiteness filler, is inherently used in flame-retardant ABS materials for flame-retardant modification. Flame-retardant ABS materials containing antimony white generally struggle to achieve a high blackness. Traditional audio housing panel components utilize natural flame-retardant ABS as the panel material, employing a spray painting process to achieve flame retardancy and high blackness. However, with increasing environmental awareness, the spray painting process is being phased out, necessitating a high-blackness flame-retardant ABS material that can be directly injection molded to achieve both environmental and aesthetic qualities. Furthermore, brominated flame retardants, particularly tetrabromobisphenol A, are easily decomposed during high-temperature processing, producing small molecules that can easily lead to appearance defects such as gas filaments. Summary of the Invention

[0004] In view of the defects of the prior art, the technical problem to be solved by the present invention is to provide an ABS composition and a preparation method and application thereof.

[0005] The ABS composition of the present invention comprises, by weight:

[0006]

[0007] Among them, carbon black with a D50 particle size of 5-15nm accounts for 25% to 67% of the total carbon black mass, and carbon black with a D50 particle size of 30-50nm accounts for 33% to 75% of the total carbon black mass. D50 particle size test standard and method: Test standard GB / T

[0008] 19077-2016, tested by laser particle size analyzer. Carbon black ensures the dyeing ability and adsorption performance of carbon black.

[0009] The structural formula of the tris(3-nitrophenyl)phosphine is: Specific preparation method: Triphenylphosphine is dissolved in a solvent (sulfuric acid) under stirring at room temperature, and then the temperature of the mixed system is lowered to below 10 °C using an ice-salt bath; then a mixed solution obtained by mixing the solvent (sulfuric acid) and nitric acid in a volume ratio of 4:1 - 6:1 is slowly added dropwise for 25 - 35 minutes, and then the reaction mixture is heated to room temperature and stirred for 5 - 8 hours. The reaction mixture is poured into ice water to precipitate the reaction product, neutralized with saturated sodium bicarbonate solution, washed with water, filtered, and dried for 6 - 8 h. Finally, tris(3-nitrophenyl)phosphine is obtained; the molar ratio of nitric acid to triphenylphosphine is 4 - 6:1.

[0010] Preferably, the brominated flame retardant is one or more of tetrabromobisphenol A, brominated epoxy resin, and decabromodiphenylethane. Preferably, the mass ratio of nano-tin dioxide to antimony trioxide in the nano-tin dioxide-coated antimony trioxide is (0.4 - 0.6):100.

[0011] Preparation method of nano-tin dioxide-coated antimony trioxide: After antimony trioxide and a silane coupling agent are blended for 2 - 5 min, an antimony trioxide complex is obtained, and then the antimony trioxide complex and nano-tin dioxide are blended for 2 - 5 min; the mass ratio of antimony trioxide to the silane coupling agent is 100:(1 - 2).

[0012] The silane coupling agent is N-(2-aminoethyl)-3-aminopropyltrimethoxysilane.

[0013] The D50 particle size of the nano-tin dioxide is 20 - 50 nm.

[0014] Preferably, the carbon black with a D50 particle size of 5 - 15 nm accounts for 33% - 50% of the total mass of the carbon black, and the carbon black with a D50 particle size of 30 - 50 nm accounts for 50% - 67% of the total mass of the carbon black.

[0015] Preferably, the composition further includes 0.1 - 1 part of an auxiliary agent.

[0016] Preferably, the auxiliary agent is at least one of an antioxidant and a lubricant.

[0017] Preferably, the antioxidant is antioxidant 1076, antioxidant 168, etc., and the lubricant is an amide lubricant (such as erucic acid amide, EBS, etc.).

[0018] Preferably, by weight parts, the composition includes:

[0019]

[0020]

[0021] A preparation method of the ABS composition of the present invention includes:

[0022] Weigh each component by weight parts, add them to the main feeding port of a twin-screw extruder after mixing, melt and extrude, pelletize, and dry to obtain an ABS composition.

[0023] Application of the ABS composition of the present invention in audio panels, security doors or microwave oven panel materials.

[0024] The present invention utilizes the high-temperature dehydration and carbonization effect of tris(3-nitrophenyl)phosphine and the high-temperature gas-phase flame retardant effect of brominated flame retardants to synergistically improve the flame retardant grade of the system. The present invention reduces the whiteness of antimony white by coating treatment of nano-tin dioxide on antimony white, and has a synergistic effect with carbon black to ensure a high blackness effect. In the present invention, carbon black can adsorb the volatiles during hot processing and is not prone to appearance air filament defects.

[0025] Beneficial effects

[0026] The ABS composition of the present invention achieves a V-0 grade flame retardant effect with a low content of brominated flame retardants added. The same content of brominated flame retardants in the system without adding synergists cannot reach V-0 flame retardance; it achieves a high blackness effect, and the L value can be lower than 26.5; it achieves a low emission effect, and the material is not prone to generate volatiles during hot processing and is not prone to appearance air filament defects. Specific embodiments

[0027] The present invention will be further described below in conjunction with specific embodiments. It should be understood that these embodiments are only used to illustrate the present invention and not to limit the scope of the present invention. In addition, it should be understood that after reading the content taught by the present invention, those skilled in the art can make various changes or modifications to the present invention, and these equivalent forms also fall within the scope defined by the appended claims of this application.

[0028] I. Raw material sources

[0029] ABS: Chi Mei PA-749;

[0030] Brominated flame retardant: tetrabromobisphenol A, Dead Sea Bromine FR-1524, Israel;

[0031] Tris(3-nitrophenyl)phosphine:

[0032] Preparation method: Triphenylphosphine is dissolved in sulfuric acid under stirring at room temperature, and then the temperature of the mixing system is lowered to below 10 °C using an ice-salt bath. Then a mixed solution of sulfuric acid and nitric acid mixed in a ratio of 5:1 is slowly added dropwise for 30 minutes, and then the reaction mixture is heated to room temperature and stirred for 6 hours. The reaction mixture is poured into ice water to precipitate the reaction product, the solution is neutralized with saturated sodium bicarbonate, washed with water, filtered, and dried for 6 h to obtain tris(3-nitrophenyl)phosphine; the molar ratio of nitric acid to triphenylphosphine is 5:1.

[0033] Phosphorus-based synergistic flame retardant: BDP, commercially available specifications

[0034] Silane coupling agent: JH-A112, N-(2-aminoethyl)-3-aminopropyltrimethoxysilane, Jinghan Chemical Industry;

[0035] Antimony trioxide: S-05N, Flash Star Antimony Industry;

[0036] Nano-tin dioxide: Xianfeng Nano, grade XFI20, D50 particle size 30nm;

[0037] Nano-tin dioxide-coated antimony trioxide-1: The mass ratio of nano-tin dioxide to antimony trioxide is 0.6:100;

[0038] Nano-tin dioxide-coated antimony trioxide-2: The mass ratio of nano-tin dioxide to antimony trioxide is 0.4:100;

[0039] Preparation method of nano-tin dioxide-coated antimony trioxide: After antimony trioxide and silane coupling agent are blended for 2-5 minutes, the antimony trioxide complex is then blended with nano-tin dioxide for 2-5 minutes; the mass ratio of silane coupling agent to antimony trioxide is 1:100.

[0040] Carbon black-1: D50 particle size = 10nm,

[0041] Carbon black-2: D50 particle size = 30nm,

[0042] Carbon black-3: D50 particle size = 15nm,

[0043] Carbon black-4: D50 particle size = 50nm,

[0044] Carbon black-5: D50 particle size = 2nm,

[0045] Carbon black-6: D50 particle size = 60nm,

[0046] Carbon black-7: The mass ratio of carbon black-1 to carbon black-2 is 1:1;

[0047] Carbon black-8: The mass ratio of carbon black-1 to carbon black-2 is 1:2;

[0048] Carbon black-9: The mass ratio of carbon black-1 to carbon black-2 is 2:1;

[0049] Carbon black-10: The mass ratio of carbon black-1 to carbon black-2 is 1:3;

[0050] Carbon black-11: The mass ratio of carbon black-3 to carbon black-4 is 1:1;

[0051] Carbon black-12: The mass ratio of carbon black-5 to carbon black-2 is 1:1;

[0052] The mass ratio of carbon black-13, carbon black-1 and carbon black-6 is 1:1;

[0053] The mass ratio of carbon black-14, carbon black-1 and carbon black-2 is 4:1;

[0054] The mass ratio of carbon black-15, carbon black-1 and carbon black-2 is 1:5;

[0055] Additives: The mass ratio of antioxidant 1076, antioxidant 168 and lubricant EBS is 2.5:2.5:3;

[0056] 2. Preparation methods of examples and comparative examples

[0057] The components are weighed in parts by weight, mixed, added to the main feed port of a twin-screw extruder, melt-extruded, granulated, and dried to obtain an ABS composition. The processing conditions for melt extrusion are as follows: zone 1 temperature 110-130° C., zone 2 temperature 180-200° C., zone 3 temperature 180-200° C., zone 4 temperature 190-210° C., zone 5 temperature 190-210° C., zone 6 temperature 180-200° C., zone 7 temperature 180-200° C., zone 8 temperature 190-210° C., zone 9 temperature 190-210° C., and a main engine speed of 300-600 rpm.

[0058] 3. Test standards and methods

[0059] Vertical burning: tested according to the standard UL94-2021 method;

[0060] Appearance silver streaks assessment: The ABS composition was melted in a single-screw injection molding machine and injection molded into a strip sample at 220°C. The sample size was 200*10*2mm, and the number of silver streaks on the sample surface was recorded.

[0061] Blackness evaluation: The ABS composition was melted in a single-screw injection molding machine and injection molded into a color plate at 220°C. The L value was measured using a colorimeter.

[0062] Table 1 Example ratio (weight parts)

[0063]

[0064] Table 2 Comparative Example Proportions (parts by weight)

[0065]

[0066]

[0067] Table 3 Performance data of the embodiment

[0068]

[0069] Table 4 shows the performance effect data of the comparative examples

[0070]

[0071] In Comparative Example 1, ordinary antimony trioxide was used, and the L value was relatively high, failing to achieve the effect of high blackness. In Comparative Examples 2-4, the particle size ratio or mass ratio was not within the range of the present invention, the L value of the material was on the high side, and the number of air filaments was relatively large. In Comparative Example 5, the proportion of large-particle-size carbon black was high, the air filament condition was good, but the blackness was insufficient. In Comparative Example 6, no large-particle-size carbon black was added, and the number of air filaments in the material was large. In Comparative Example 7, no small-particle-size carbon black was added, the L value of the material was on the high side, and the effect of high blackness could not be achieved. In Comparative Examples 8-9, a single type of brominated flame retardant or tris(3-nitrophenyl)phosphine was used, and the flame retardant grade could not reach V-0

Claims

1. An ABS composition, characterized in that: In parts by weight, the components include: ABS 73-78 copies; 12-16 parts of brominated flame retardant; 3-8 parts of tri(3-nitrophenyl)phosphine; 2-7 parts of nano-tin dioxide coated antimony trioxide; Carbon black 0.5-3 parts; The carbon black with a D50 particle size of 5-15 nm accounts for 25% to 67% of the total carbon black mass, and the carbon black with a D50 particle size of 30-50 nm accounts for 33% to 75% of the total carbon black mass; wherein the mass ratio of nano-tin dioxide to antimony trioxide in the nano-tin dioxide-coated antimony trioxide is (0.4-0.6):

100.

2. The ABS composition according to claim 1, characterized in that: The brominated flame retardant is one or more of tetrabromobisphenol A, brominated epoxy, and decabromodiphenylethane.

3. The ABS composition according to claim 1, characterized in that: In the carbon black, carbon black with a D50 particle size of 5-15 nm accounts for 33% to 50% of the total carbon black mass, and carbon black with a D50 particle size of 30-50 nm accounts for 50% to 67% of the total carbon black mass.

4. The ABS composition according to claim 1, characterized in that: The components also include 0.1-1 parts of auxiliary agents.

5. The ABS composition according to claim 4, characterized in that: The auxiliary agent is at least one of an antioxidant and a lubricant.

6. The ABS composition according to claim 1, characterized in that: In parts by weight, the components include: ABS 74-76 copies; 13-15 parts of brominated flame retardant; 5-7 parts of tri(3-nitrophenyl)phosphine; 3-5 parts of nano-tin dioxide coated antimony trioxide; 1-2 parts of carbon black.

7. A method for preparing the ABS composition according to claim 1, comprising: The components are weighed in parts by weight, mixed and added to the main feed port of a twin-screw extruder, melt-extruded, granulated and dried to obtain an ABS composition.

8. Use of the ABS composition according to claim 1 in audio panels, security doors or microwave oven panel materials.

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