ABS high-rubber powder and preparation method thereof, and flame-retardant ABS composition and preparation method thereof

Abstract

The invention discloses an ABS high-rubber powder, which comprises the following components in terms of weight percentage of the ABS high-rubber powder: the ABS high-rubber powder has a shell layer, an intermediate layer and an outer layer, with 1-5wt% antimony trioxide as a core, 45-63.5wt% of polybutadiene and 0.5-2wt% of a reaction product of a metal salt functional monomer containing dithioamino and vinyloxyalkyl as an intermediate layer, and SAN grafted on the surface of polybutadiene as an outer layer, wherein SAN accounts for 35-50wt% of the ABS high-rubber powder. The present invention mainly forms the ABS high-rubber powder by modifying polybutadiene latex with antimony trioxide as a core and further grafting SAN. The ABS high-rubber powder of the present invention has the advantages of good flame retardancy, good mechanical properties and high gloss, and is suitable for preparing a flame-retardant ABS composition.

Description

Technical Field

[0001] The invention relates to the technical field of polymer materials, in particular to ABS high-rubber powder and a preparation method thereof and a flame-retardant ABS composition. Background Art

[0002] With the development of society, people have higher and higher requirements for products. When the performance is similar, they prefer products with beautiful appearance. Therefore, high-gloss ABS is used in many daily necessities, tools and decorations close to people's lives, such as LED display frames and bases, refrigerator shells, household kitchen countertops and external parts of electronic products. However, the oxygen index of ABS resin is only 8.3-20, which is a flammable polymer material. When used in various electronic and electrical products with flame retardant requirements, its flame retardancy needs to be improved to meet the requirements of safety and fire protection. Therefore, the research on high-gloss flame-retardant ABS is becoming more and more popular.

[0003] Antimony trioxide is a commonly used flame retardant synergist that gives ABS excellent flame retardant properties, but it will deteriorate the mechanical properties of ABS materials, especially the impact performance system, and seriously affect the gloss of the material.

[0004] Patent CN103613899B discloses a flame-retardant ABS alloy material, which adds nano-antimony trioxide as a flame-retardant synergist to obtain a high-gloss and high-impact flame-retardant ABS alloy material, but adds methyl methacrylate-butadiene-styrene terpolymer powder as a toughening agent, which is costly. Patent CN 102492170 B discloses an antimony trioxide masterbatch and its preparation method, which uses polyolefin as a carrier, adds a dispersant, and extrudes after mixing to obtain a high-concentration masterbatch, which has complex processing steps and high costs. Summary of the invention

[0005] The object of the present invention is to provide an ABS high-rubber powder with antimony trioxide as a core, which has good flame retardancy, good mechanical properties and high gloss.

[0006] Another object of the present invention is to provide a preparation method and application of ABS high-rubber powder.

[0007] The present invention is achieved through the following technical solutions:

[0008] The invention discloses an ABS high-rubber powder, which comprises the following components in terms of weight percentage of the ABS high-rubber powder: the ABS high-rubber powder of the invention comprises a shell layer, an intermediate layer and an outer layer, with 1-5wt% of antimony trioxide as a core, 45-63.5wt% of a reaction product of polybutadiene and 0.5-2wt% of a metal salt functional monomer containing dithioamino and vinyloxyalkyl as the intermediate layer, and SAN grafted on the surface of the polybutadiene as the outer layer, wherein the SAN accounts for 35-50wt% of the ABS high-rubber powder.

[0009] Preferably, the ABS high-rubber powder includes the following components in weight percentage: the ABS high-rubber powder has a shell layer, a middle layer and an outer layer, with 2-4wt% antimony trioxide as the core, 50-57.5wt% of the reaction product of polybutadiene and 0.5-2wt% of the metal salt functional monomer containing dithioamino and vinyloxyalkyl as the middle layer, and SAN grafted on the surface of polybutadiene as the outer layer, wherein SAN accounts for 40-46wt% of the ABS high-rubber powder.

[0010] The average particle size of antimony trioxide is 5-100 nm, preferably 10-70 nm, and is measured by a particle size analyzer.

[0011] A metal salt functional monomer containing dithioamino and vinyloxyethyl reacts with antimony trioxide to generate dithiocarbamate antimony salt, which is adsorbed on the surface of antimony trioxide to achieve coating. The vinyloxyethyl initiates butadiene polymerization and reacts with the above functional monomer to graft polybutadiene on the surface of antimony trioxide.

[0012] The metal salt functional monomer containing dithioamino group and vinyloxyalkyl group is selected from at least one of N,N-(divinyloxyalkyl)dithiocarbamate metal salt, N-(vinyloxyalkyl)dithiocarbamate metal salt, bis[N-(vinyloxyalkyl)dithiocarbamate] metal salt, and bis[N,N-(divinyloxyalkyl)dithiocarbamate] metal salt;

[0013] The N,N-(divinyloxyalkyl)dithiocarbamate metal salt is selected from at least one of N,N-(divinyloxymethyl)dithiocarbamate potassium, N,N-(divinyloxymethyl)dithiocarbamate sodium, N,N-(divinyloxyethyl)dithiocarbamate potassium, and N,N-(divinyloxyethyl)dithiocarbamate sodium;

[0014] Among them, the chemical formula of potassium N,N-(divinyloxyethyl)dithiocarbamate is as follows:

[0015]

[0016] The N-(vinyloxyalkyl)dithiocarbamate metal salt is selected from at least one of potassium N-(vinyloxyethyl)dithiocarbamate, sodium N-(vinyloxyethyl)dithiocarbamate, potassium N-(vinyloxymethyl)dithiocarbamate, and sodium N-(vinyloxymethyl)dithiocarbamate;

[0017] Among them, the chemical formula of potassium N-(vinyloxyethyl)dithiocarbamate is as follows:

[0018]

[0019] The bis[N-(vinyloxyalkyl)dithiocarbamate] metal salt is at least one selected from calcium bis[N-(vinyloxyethyl)dithiocarbamate], copper bis[N-(vinyloxyethyl)dithiocarbamate], zinc bis[N-(vinyloxyethyl)dithiocarbamate], calcium bis[N-(vinyloxymethyl)dithiocarbamate], copper bis[N-(vinyloxymethyl)dithiocarbamate], and zinc bis[N-(vinyloxymethyl)dithiocarbamate];

[0020] The chemical formula of calcium bis[N-(vinyloxyethyl)dithiocarbamate] is as follows:

[0021]

[0022] The bis[N,N-(divinyloxyalkyl)dithiocarbamate] metal salt is at least one selected from calcium bis[N,N-(divinyloxyethyl)dithiocarbamate], copper bis[N,N-(divinyloxyethyl)dithiocarbamate], zinc bis[N,N-(divinyloxyethyl)dithiocarbamate], calcium bis[N,N-(divinyloxymethyl)dithiocarbamate], copper bis[N,N-(divinyloxymethyl)dithiocarbamate], and zinc bis[N,N-(divinyloxymethyl)dithiocarbamate];

[0023] The chemical formula of calcium bis[N,N-(divinyloxyethyl)dithiocarbamate] is as follows:

[0024]

[0025] Preferably, the metal salt functional monomer containing dithioamino group and vinyloxyalkyl group is selected from metal salts of N-(vinyloxyalkyl)dithiocarbamate; more preferably potassium N-(vinyloxyalkyl)dithiocarbamate.

[0026] The preparation method of ABS high-rubber powder of the present invention comprises the following steps:

[0027] Preparation of polybutadiene latex: by weight, add 10-20 parts of organic solvent, 1-5 parts of metal salt functional monomer containing dithioamino group and vinyloxyethyl group, 1-5 parts of antimony trioxide, and 60-100 parts of deionized water into a reactor, stir and heat, then add 80-120 parts of butadiene, 1-8 parts of emulsifier, 0.1-3 parts of electrolyte, 0.1-3 parts of chain transfer agent, 0.1-3 parts of initiator and 20-30 parts of deionized water, continue polymerization reaction, cool the reactor to room temperature after the reaction is completed, and filter to obtain polybutadiene latex;

[0028] The reaction time of the heat preservation reaction at 50-80° C. is 0.5-1 hour; and the judgment standard for the completion of the polymerization reaction of the polybutadiene latex is 250nm≤polybutadiene latex particle size≤500nm.

[0029] The surface of nano antimony trioxide is partially dissolved and dispersed by alcohol organic solvents, and metal salt functional monomers containing dithioamino groups and vinyloxyalkyl groups react with antimony trioxide to generate dithiocarbamate antimony salts, so that the metal salt functional monomers containing dithioamino groups and vinyloxyalkyl groups are adsorbed on the surface of antimony trioxide, thereby achieving the pre-dispersion and surface functionalization of nano antimony trioxide. The double bonds in the vinyloxyalkyl groups in the above functional monomers adsorbed on the surface are initiated by an initiator to polymerize with part of butadiene, and initiate emulsion polymerization of butadiene, thereby achieving the coating of butadiene rubber on the surface of antimony trioxide, and the monomers are emulsion copolymerized to form a uniform latex, and the viscosity of the system decreases rapidly in a step-like manner at a high conversion rate, thereby obtaining a low-viscosity antimony trioxide core polybutadiene latex.

[0030] The preparation of butadiene latex is the key to the technical solution of this patent. The subsequent preparation of ABS high-rubber powder is a conventional process of SAN grafting, coagulation, dehydration, drying, and then blending with SAN.

[0031] Specifically, the preparation method of ABS high-rubber powder is as follows: add the above 60 parts of polybutadiene latex to a reactor, add 2-4 parts of ferrous sulfate to the reactor and stir evenly, heat the reactor to 65-70°C, add 0.1-0.5 parts of cumene hydroperoxide (initiator), 35-70 parts of acrylonitrile / styrene, 0.1-0.3 parts of tert-dodecyl mercaptan, 1-3 parts of sodium dodecyl sulfonate and 50-70 parts of deionized water, continue to react for 4-6 hours after heating, and obtain grafted latex. Take the grafted latex and add it to a coagulation reactor, start stirring and heat to 70-80°C, gradually add ethyl sulfuric acid thereto, add it for 1-4 hours, heat it to 88-95°C and keep the temperature for 1-5 hours, filter the obtained coagulated latex, dry it, and then blend it with SAN through a twin-screw extruder to obtain ABS high-rubber powder.

[0032] The optional organic solvent is selected from at least one of methanol, ethanol, n-propanol, isopropanol, n-butanol, isopentanol and ethylene glycol.

[0033] The emulsifier is selected from anionic emulsifiers; the anionic emulsifier is selected from at least one of potassium oleate, potassium disproportionate rosin acid, sodium dodecyl sulfate, sodium dodecylbenzene sulfonate, and dioctyl sodium sulfosuccinate;

[0034] The electrolyte is selected from at least one of potassium bicarbonate, potassium carbonate, sodium bicarbonate, sodium carbonate and sodium tripolyphosphate.

[0035] The chain transfer agent is selected from at least one of n-butyl mercaptan, n-octyl mercaptan, n-dodecyl mercaptan and tert-dodecyl mercaptan.

[0036] The initiator includes (but is not limited to): hydrogen peroxide compounds, such as tert-butyl peroxide (di-tert-butyl peroxide, tert-butyl hydroperoxide, 2,5-dimethyl-2,5-bis(tert-butylperoxy)hexane), peroxy ketal compounds, such as 1,1-bis-tert-butylperoxy-3,3,5-trimethylcyclohexane, 2,2-bis(4,4-di(tert-butylperoxy)cyclohexyl)propane, alkanes, etc.; peroxyester compounds, such as tert-butyl peroxypivalate, 2,5-dimethyl-2,5-di(2-ethylhexanol peroxide)hexane, etc.; peroxyketal compounds, such as 4,4-diperoxytert-butyl-pentanoic acid-n-butyl ester, etc.; peroxycarbonate compounds, such as 2-ethylhexyl tert-amyl peroxycarbonate, 2-ethylhexyl tert-butyl peroxycarbonate, etc.; or azo compounds with nitro and cyclohexane, etc.

[0037] The ABS high-rubber powder of the present invention is used for preparing a flame-retardant ABS composition, especially for the household appliance industry with high gloss and flame-retardant requirements, such as household appliance shells.

[0038] The flame retardant ABS composition comprises the following components in parts by weight:

[0039] ABS high glue powder 20-60 parts;

[0040] 40-80 parts of AS resin;

[0041] 5-25 parts of brominated flame retardant;

[0042] The brominated flame retardant is one or more of tetrabromobisphenol A, decabromodiphenylethane, 2,4,6-tribromotriphenoxy-1,3,5-triazine, ethylene-(bis-tetrabromophthalimide), brominated epoxy resin, and tetrabromophthalic acid-(2-ethylhexyl) ester.

[0043] It may also contain 0.1-1 part of antioxidant and 0.1-1 part of lubricant. The lubricant is one or a combination of two of dimethyl silicone oil lubricant, silicone powder, pentaerythritol stearate, polyethylene wax, ethylene bis stearamide or magnesium stearate.

[0044] The antioxidant is a phosphite antioxidant or a hindered phenol antioxidant.

[0045] The present invention has the following beneficial effects:

[0046] The core of the polybutadiene latex of the present invention is nano-antimony trioxide, which is then prepared into ABS high-rubber powder, and then a flame-retardant ABS composition is prepared by blending. The good dispersion of the high-rubber powder in the ABS resin enables the uniform dispersion of the nano antimony trioxide in the resin material. The flame-retardant ABS resin prepared by the polybutadiene latex prepared by the method provided by the present invention has a very high surface gloss and good toughness, and is particularly suitable for the home appliance industry with high gloss and flame retardancy requirements. DETAILED DESCRIPTION

[0047] The present invention is described in detail below in conjunction with specific embodiments. The following embodiments will help those skilled in the art to further understand the present invention, but are not intended to limit the present invention in any form. It should be noted that, for those of ordinary skill in the art, several variations and improvements may be made without departing from the concept of the present invention. These all belong to the protection scope of the present invention.

[0048] The sources of raw materials required for the preparation of ABS used in the present invention are as follows:

[0049] Ethanol: industrial grade, 99.5%, Guangzhou Reagent;

[0050] Isopropanol: AR, ≥99.7%, Guangzhou Reagent;

[0051] Antimony trioxide: <250 nm (TEM), purity ≥99.9%, Aladdin, and then screened to obtain raw materials with different average particle sizes;

[0052] Potassium oleate: purity 98%, Aladdin;

[0053] Potassium disproportionate rosin acid: purity 98%, Aladdin;

[0054] Potassium bicarbonate: industrial grade, Uni-D;

[0055] Potassium carbonate: industrial grade, Ulead;

[0056] n-Butyl mercaptan: purity 99.5%, Aladdin;

[0057] n-Dodecyl mercaptan: purity 98%, Chevron; tert-butyl peroxide: di-tert-butyl peroxide, purity 97%, Aladdin;

[0058] Tert-butyl peroxypivalate: initiator LQ-TBPV, Lanzhou Auxiliary Agent Factory;

[0059] Embodiment and comparative example Preparation method of ABS high-rubber powder: Preparation of polybutadiene latex: by weight, take 15 parts of organic solvent (isopropanol), metal salt functional monomer containing dithioamino group and vinyloxyalkyl group (weight content see table), antimony trioxide (weight content and average particle size see table), 80 parts of deionized water, add into the reactor, stir and heat, keep warm at 65°C for 0.5-1 hour, then add 100 parts of butadiene (gaseous butadiene does not react completely, the weight content of polybutadiene in the final product is shown in the table), 4 parts of emulsifier (potassium oleate), 1 part of electrolyte (potassium bicarbonate), 1.2 parts of chain transfer agent (n-butyl mercaptan), initiator (tert-butyl The polymerization reaction is continued. When the particle size of the polybutadiene latex is about 300 nm, the reactor is cooled to room temperature and the polybutadiene latex is obtained by filtration. The preparation method of ABS high-rubber powder is as follows: 60 parts of the polybutadiene latex obtained by the above method are added to a reactor, and 2.5 parts of ferrous sulfate are added to the reactor and stirred evenly, the reactor is heated to 67°C, and 0.2 parts of cumene hydroperoxide, acrylonitrile / styrene (weight content see table), 0.15 parts of tert-dodecyl mercaptan, 1.5 parts of sodium dodecyl sulfonate and 60 parts of deionized water are added, and the addition is continued for 2 hours. After the heating is completed, the reaction is continued for 5 hours to obtain a grafted latex. Take 1000 parts of grafted latex and add it into a coagulation reactor, start stirring and heat to 75°C, gradually add 5% sulfuric acid, add it within 2 hours, and raise the temperature to 91°C and maintain the temperature for 3 hours. The obtained coagulated latex is filtered through a 325-mesh filter and dried in a fluidized bed dryer at 60°C for 6 hours, and then mixed with SAN through a twin-screw extruder to obtain ABS high-rubber powder with a moisture content of <1%.

[0060] The metal salt functional monomers containing dithioamino groups and vinyloxyalkyl groups (referred to as functional monomers in the table) in the experiment are:

[0061] Functional monomer A: potassium N-(vinyloxyethyl) dithiocarbamate, homemade;

[0062] Functional monomer B: sodium N-(vinyloxyethyl) dithiocarbamate, homemade;

[0063] Synthesis of A and B: 11.2 g (0.2 mol) potassium hydroxide (0.2 mol sodium hydroxide for functional monomer B) was added to 34.8 g (0.4 mol) vinyloxyethylamine, and then 15.2 g (0.2 mol) carbon disulfide was added. The mixture was stirred at 40-45°C for 5 hours. Excess vinyloxyethylamine was evaporated. The crystalline residue was washed with 30 ml of ethanol and then with 15 ml of ether and dried to obtain 31.8 g of potassium N-vinyloxyethyl dithiocarbamate, with a yield of 79% (when potassium hydroxide was replaced with sodium hydroxide, sodium N-vinyloxyethyl dithiocarbamate was obtained, with a yield of 76%).

[0064] Functional monomer C: zinc bis[N-(vinyloxyethyl)dithiocarbamate], homemade;

[0065] Synthesis method: Potassium N-(vinyloxyethyl)dithiocarbamate is replaced with zinc chloride in an aqueous medium to obtain zinc bis[N-(vinyloxyethyl)dithiocarbamate].

[0066] Functional monomer D: Potassium N,N-diethyldithiocarbamate was purchased from Guangzhou Jiatu;

[0067] Table 1: Weight percentage of each component of ABS high-rubber powder in ABS high-rubber powder, and types of functional monomers

[0068] ABS-1 ABS-2 ABS-3 ABS-4 ABS-5 ABS-6 Functional monomer type A B C D A A Functional monomer, wt% 0.5 0.5 0.5 0.5 0.5 0.5 Average particle size of antimony trioxide, nm 66.3 66.3 66.3 66.3 5 12.5 Antimony trioxide, wt% 2.5 2.5 2.5 2.5 2.5 2.5 Polybutadiene, wt% 52 52 52 52 52 52 Grafted SAN, wt% 45 45 45 45 45 45

[0069] Table 1 continued:

[0070] ABS-7 ABS-8 ABS-9 ABS-10 ABS-11 ABS-12 Functional monomer type A A A A A - Functional monomer, wt% 0.5 0.5 0.5 0.5 0.5 - Average particle size of antimony trioxide, nm 97.8 66.3 66.3 66.3 66.3 66.3 Antimony trioxide, wt% 2.5 1 2 4 5 3 Polybutadiene, wt% 52 63 57.5 50 45 52 Grafted SAN, wt% 45 35.5 40 45.5 49.5 45

[0071] Embodiment and comparative example Preparation method of flame-retardant ABS composition: According to the ratio, ABS high rubber powder, AS resin, 2,4,6-tribromotriphenoxy-1,3,5-triazine, antioxidant and lubricant are uniformly mixed, and extruded and granulated by a twin-screw extruder (extrusion temperature is 185-220°C, screw speed is 300r / min, screw aspect ratio is 25:1) to obtain a flame-retardant ABS composition.

[0072] Various test methods:

[0073] (1) Glossiness: tested according to GB8807-88 (20 degree angle);

[0074] (2) Impact strength: Tested according to GB / T1843-2008; 4.0 mm thickness, notch

[0075] (3) Flame retardancy: According to the UL94-2000 test, the thickness of the specimens is 1.6 mm.

[0076] 2,4,6-Tribromotriphenoxy-1,3,5-triazine: commercially available;

[0077] Antioxidants: Hindered phenolic antioxidants, 1076, Lianlong;

[0078] Lubricant: Pentaerythritol stearate, Kao, Japan.

[0079] Commercially available ABS high-glue powder: ABS POW HR181, Kumho, South Korea;

[0080] AS resin: SAN 350, Kumho, Korea;

[0081] The contents of each component in the flame retardant ABS composition of the embodiments and comparative examples are as follows:

[0082] 50 parts of ABS high-rubber powder, 40 parts of AS resin, 15 parts of 2,4,6-tribromotriphenoxy-1,3,5-triazine, 0.5 parts of antioxidant, 0.5 parts of lubricant, and Comparative Example 1 also contains 1.25 parts of antimony trioxide.

[0083] Table 2: Selection and test results of ABS in flame-retardant ABS compositions of Examples and Comparative Examples

[0084] Example 1 Example 2 Example 3 Example 4 Selection of ABS high glue powder ABS-1 ABS-2 ABS-3 ABS-5 Glossiness 88.5 86.5 84.8 91.6 <![CDATA[Impact strength, kJ / m 2 > 30 28 25 29 Flame retardant V-0 V-0 V-1 V-1

[0085] As can be seen from Examples 1-3, the functional monomer is preferably a metal salt of N-(vinyl)oxyethyldithiocarbamate, and more preferably potassium N-(vinyl)oxyethyldithiocarbamate.

[0086] Table 2 continued:

[0087] Example 5 Example 6 Example 7 Example 8 Example 9 Example 10 Selection of ABS high glue powder ABS-6 ABS-7 ABS-8 ABS-9 ABS-10 ABS-11 Glossiness 89.0 88.3 90.4 88.5 87.6 85.7 <![CDATA[Impact strength, kJ / m 2 > 31 27 24 28 26 22 Flame retardant V-0 V-1 V-1 V-0 V-0 V-0

[0088] It can be seen from Examples 1 / 4-6 that the average particle size of antimony trioxide is preferably 10-70 microns.

[0089] It can be seen from Examples 1 / 7-10 that, from the perspective of impact strength, the impact strength is higher when the antimony trioxide content is 2-4wt%, the polybutadiene content is 50-57.5wt%, the functional monomer is 0.5-2wt%, and the SAN content is 40-46wt%.

[0090] Table 2 continued:

[0091] Comparative Example 1 Comparative Example 2 Comparative Example 3 Selection of ABS high glue powder Commercially available ABS ABS-4 ABS-12 Glossiness 75.6 63.1 60.6 <![CDATA[Impact strength, kJ / m 2 > 23 21 19 Flame retardant V-2 V-2 V-2

[0092] It can be seen from Comparative Example 1 that the conventional ABS composition can only achieve flame retardancy of V-2 and has low gloss.

[0093] It can be seen from Comparative Example 2 that potassium N,N-diethyldithiocarbamate does not contain ethylene double bonds, resulting in poor coating of antimony trioxide during the butadiene polymerization process, and thus poor flame retardancy and impact resistance.

Claims

1. An ABS high-rubber powder, characterized in that: The ABS high-rubber powder comprises the following components in weight percentage: the ABS high-rubber powder has a shell layer, a middle layer and an outer layer, with 1-5wt% of antimony trioxide as the core, 45-63.5wt% of polybutadiene and 0.5-2wt% of the reaction product of a metal salt functional monomer containing dithioamino and vinyloxyalkyl as the middle layer, and SAN grafted on the surface of polybutadiene as the outer layer, wherein SAN accounts for 35-50wt% of the ABS high-rubber powder.

2. The ABS high-rubber powder according to claim 1, characterized in that: The ABS high-rubber powder comprises the following components in weight percentage: the ABS high-rubber powder has a shell layer, a middle layer and an outer layer, with 2-4wt% of antimony trioxide as the core, 50-57.5wt% of the reaction product of polybutadiene and 0.5-2wt% of the metal salt functional monomer containing dithioamino and vinyloxyalkyl as the middle layer, and SAN grafted on the surface of polybutadiene as the outer layer, wherein SAN accounts for 40-46wt% of the ABS high-rubber powder.

3. The ABS high-rubber powder according to claim 1, characterized in that: The average particle size of antimony trioxide is 5-100 nm.

4. The ABS high-rubber powder according to claim 3, characterized in that: The average particle size of antimony trioxide is 10-70nm.

5. The ABS high-rubber powder according to claim 1, characterized in that: The metal salt functional monomer containing dithioamino group and vinyloxyalkyl group is selected from at least one of N,N-(divinyloxyalkyl) dithiocarbamate metal salt, N-(vinyloxyalkyl) dithiocarbamate metal salt, bis[N-(vinyloxyalkyl) dithiocarbamate] metal salt, bis[N,N-(divinyloxyalkyl) dithiocarbamate] metal salt; the N,N-(divinyloxyalkyl) dithiocarbamate metal salt is selected from at least one of N,N-(divinyloxymethyl) dithiocarbamate potassium, N,N-(divinyloxymethyl) dithiocarbamate sodium, N,N-(divinyloxyethyl) dithiocarbamate potassium, and N,N-(divinyloxyethyl) dithiocarbamate sodium; the N-(vinyloxyalkyl) dithiocarbamate metal salt is selected from N-(vinyloxyethyl) dithiocarbamate The bis[N-(vinyloxyethyl)dithiocarbamate] metal salt is selected from at least one of bis[N-(vinyloxyethyl)dithiocarbamate] calcium, bis[N-(vinyloxyethyl)dithiocarbamate] copper, bis[N-(vinyloxyethyl)dithiocarbamate] zinc, bis[N-(vinyloxymethyl)dithiocarbamate] calcium, bis[N-(vinyloxymethyl)dithiocarbamate] copper, bis[N-(vinyloxymethyl)dithiocarbamate] zinc; the bis[N,N-(divinyloxyalkyl)dithiocarbamate] metal salt is selected from at least one of bis[N,N-(divinyloxyethyl)dithiocarbamate] At least one of calcium, copper bis[N,N-(divinyloxyethyl)dithiocarbamate], zinc bis[N,N-(divinyloxyethyl)dithiocarbamate], calcium bis[N,N-(divinyloxymethyl)dithiocarbamate], copper bis[N,N-(divinyloxymethyl)dithiocarbamate], and zinc bis[N,N-(divinyloxymethyl)dithiocarbamate].

6. The ABS high-rubber powder according to claim 5, characterized in that: The metal salt functional monomer containing dithioamino group and vinyloxyalkyl group is selected from N-(vinyloxyalkyl) dithiocarbamic acid metal salt.

7. The ABS high-rubber powder according to claim 6, characterized in that: The metal salt functional monomer containing dithioamino group and vinyloxyalkyl group is selected from potassium N-(vinyloxyalkyl)dithiocarbamate.

8. A flame retardant ABS composition, characterized in that: By weight, it comprises 40-80 parts of AS resin, 20-60 parts of ABS high-rubber powder according to any one of claims 1 to 7, and 5-25 parts of brominated flame retardant.

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