ABS (Acrylonitrile Butadiene Styrene) resin and preparation method thereof

Abstract

The invention provides ABS (Acrylonitrile Butadiene Styrene) resin and a preparation method thereof. The method comprises the following steps: grafting a hindered phenol antioxidant containing two unsaturated double bonds on the surface of a polybutadiene rubber core layer to form a functional layer, and grafting styrene and acrylonitrile on the surface of the functional layer to prepare the ABS latex with the multilayer structure. The ABS resin prepared by the invention has excellent oxidation resistance, and the impact resistance, tensile strength and bending strength of the ABS resin are maintained while the b * value of the resin is reduced.

Description

Technical Field

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

[0002] ABS resin is a thermoplastic polymer material that is easy to process and has excellent performance. It has a "sea-island" structure with polybutadiene rubber as the dispersed phase and a copolymer resin of styrene and acrylonitrile as the continuous phase, and is commonly used in automobiles, electronics, and electrical appliances.

[0003] There are double bonds in the polybutadiene of ABS resin. Since the double bonds are easily broken under the influence of external conditions such as shear, heat, oxygen, and impurities, the ABS resin will undergo aging degradation, ultimately leading to a decrease in the mechanical properties of ABS and yellowing and other phenomena.

[0004] During the emulsion polymerization process of ABS, hindered phenol antioxidants are usually added for simple physical blending to delay the aging phenomenon of ABS resin. Chen Jie (Research on the Application of Polymer Hindered Phenol Antioxidant CPL in ABS Resin, Henan Chemical Industry, 2021) studied the influence of adding polymer hindered phenol antioxidant CPL to ABS resin on the product performance. It was found that the reason for the decrease in tensile strength and impact strength was the addition of polymer hindered phenol antioxidant CPL, which reduced the tensile strength and impact strength of the resin. The reason was that the antioxidant partially damaged the original crystalline structure of the material, thus reducing the mechanical properties of the material.

[0005] In summary, in the field of ABS resin, the physical blending of emulsion antioxidants and ABS latex has poor antioxidant dispersion effect, and partial loss of antioxidants will occur during the subsequent coagulation and washing process of rubber powder, reducing the anti-aging effect, resulting in an increase in the b* value of the resin and a decrease in mechanical properties. Summary of the Invention

[0006] Aiming at the above problems existing in the prior art, one of the purposes of the present invention is to provide a preparation method of polybutadiene latex, which reduces the b* value of ABS resin, and while greatly improving the whiteness of ABS resin, ensures the mechanical properties such as the impact resistance of ABS resin.

[0007] To achieve the above invention purpose, the technical scheme adopted by the present invention is as follows:

[0008] A preparation method of a multi-layer ABS latex, the method grafts a hindered phenol antioxidant containing two unsaturated double bonds on the surface of the polybutadiene rubber core layer to form a functional layer, and then grafts styrene and acrylonitrile on the surface of the functional layer to prepare a multi-layer structure ABS latex.

[0009] In an embodiment of the present invention, the method comprises the following steps:

[0010] S1: Add polybutadiene latex and water into the reactor, mix and keep warm.

[0011] S2: Stir and emulsify the hindered phenol antioxidant, emulsifier, electrolyte, initiator and water.

[0012] S3: Add the emulsion in S2 into the reactor in S1 for reaction, keep warm, and prepare polybutadiene latex.

[0013] S4: Add the reducing agent into the reactor in S3, add the emulsifier, initiator, styrene and acrylonitrile, keep warm, and prepare the multi-layer structured ABS latex.

[0014] Currently, the common method of introducing antioxidants into the resin system is physical blending. After the ABS emulsion graft polymerization is completed, an emulsion-type antioxidant is added, and the ABS latex and the antioxidant are mixed by stirring. The dispersion effect of the emulsion-type antioxidant depends on the particle size, the dispersion effect of the antioxidant is poor, and part of the antioxidant will be lost during the subsequent coagulation and washing process of the rubber powder, reducing the anti-aging effect. In the present invention, a hindered phenol antioxidant containing two unsaturated double bonds is grafted on the surface of the PB rubber core layer to form an antioxidant layer, and then styrene acrylonitrile is grafted on the surface of the antioxidant layer to prepare ABS rubber powder, which has a unique multi-layer structure. Since the aging of ABS resin mainly stems from the double bonds in the core layer PB being easily damaged by light, heat, oxygen, etc., grafting antioxidants on the outer layer of the PB core can comprehensively and effectively protect the PB double bonds, preventing the rubber powder from aging and yellowing at the source. The ABS resin prepared therefrom has excellent antioxidant properties, reducing the b* value of the resin while maintaining its impact resistance, tensile strength and flexural strength.

[0015] In one embodiment of the present invention, in S1, 60-100 parts by weight of polybutadiene latex and 30-50 parts by weight of water are used.

[0016] In one embodiment of the present invention, the particle size of the polybutadiene latex in S1 is 200-400 nm, preferably 250-350 nm.

[0017] In one embodiment of the present invention, the heat preservation temperature in S1 is 60°C - 80°C.

[0018] In one embodiment of the present invention, in S2, 2-10 parts by weight of hindered phenol antioxidant, 3-10 parts by weight of emulsifier, 0.1-3 parts by weight of electrolyte, 0.1-3 parts by weight of initiator, and 60-80 parts by weight of water are used.

[0019] In one embodiment of the present invention, the hindered phenol antioxidant in S2 has the structure shown in formula (1):

[0020]

[0021] In formula (1), the group R 1 , R 3 , R 5 are each independently selected from any one of hydrogen, C 1-10 linear chain, C 1-10 branched alkyl; the groups R 2 , R 4 are each independently selected from hydrogen, C 1-6 linear hydrocarbon group, C 1-6 branched hydrocarbon group, C 3-6 isomerized hydrocarbon group, and there are two unsaturated carbon-carbon double bonds in the groups R 2 , R 4 .

[0022] In one embodiment of the present invention, the emulsifier in S2 is an anionic emulsifier, preferably one or more of potassium oleate, potassium disproportionated rosin, sodium dodecyl sulfate, sodium dodecyl benzene sulfonate, and sodium dioctyl sulfosuccinate.

[0023] In one embodiment of the present invention, the electrolyte in S2 is an inorganic salt, preferably one or more of potassium bicarbonate, potassium carbonate, sodium bicarbonate, sodium carbonate, and sodium tripolyphosphate.

[0024] In one embodiment of the present invention, the initiator in S2 is selected from inorganic peroxides and / or organic peroxides, preferably one or more of potassium persulfate, sodium persulfate, ammonium persulfate, dicumyl peroxide, and cumene hydroperoxide.

[0025] In one embodiment of the present invention, the addition method of the emulsion in S3 is dropwise addition; preferably, the dropwise addition time is 2 - 4 h.

[0026] In one embodiment of the present invention, the heat preservation temperature in S3 is 70 - 90 °C, and the heat preservation time is 0.5 - 5 h.

[0027] In one embodiment of the present invention, in S4, the reducing agent is 0.1 - 1 part by weight, the emulsifier is 0.5 - 3 parts by weight, the initiator is 0.1 - 0.5 part by weight, styrene is 30 - 80 parts by weight, and acrylonitrile is 10 - 30 parts by weight;

[0028] In one embodiment of the present invention, the reducing agent in S4 is one or more of ferrous sulfate, glucose, sodium pyrophosphate, ethylenediaminetetraacetic acid disodium salt, and sodium formaldehyde sulfoxylate;

[0029] In one embodiment of the present invention, the emulsifier in S4 is an anionic emulsifier, preferably one or more of potassium oleate, potassium disproportionated rosin, sodium dodecyl sulfate, sodium dodecyl benzene sulfonate, and sodium dioctyl sulfosuccinate.

[0030] In one embodiment of the present invention, the initiator in S4 is selected from inorganic peroxides and / or organic peroxides, preferably one or more of potassium persulfate, sodium persulfate, ammonium persulfate, dicumyl peroxide, and cumene hydroperoxide.

[0031] In one embodiment of the present invention, the emulsifier, initiator, styrene, and acrylonitrile in S4 are added dropwise; preferably, the dropping time is 2 - 5 h.

[0032] In one embodiment of the present invention, the heat preservation temperature in S4 is 70 - 90 °C, and the heat preservation time is 0.5 - 3 h.

[0033] Another object of the present invention is to provide a multi - layer ABS latex.

[0034] A multi - layer ABS latex, the latex is prepared by the above - mentioned preparation method, and the latex has a multi - layer structure; preferably, in the multi - layer latex, a hindered phenol antioxidant functional layer containing two unsaturated double bonds is grafted on the surface of the polybutadiene rubber core layer, and styrene and acrylonitrile are grafted on the surface of the functional layer.

[0035] Another object of the present invention is to provide a polybutadiene latex.

[0036] A polybutadiene latex, the latex is obtained by the above - mentioned preparation method, and a hindered phenol antioxidant functional layer containing two unsaturated double bonds is grafted on the surface of the polybutadiene rubber core layer in the latex.

[0037] Another object of the present invention is to provide a use of the multi - layer ABS latex

[0038] A use of the multi - layer ABS latex, the latex is the latex obtained by the above - mentioned preparation method, or the above - mentioned latex, and the latex is used to prepare ABS resin applied to the fields of household appliances, office supplies, and automobiles, preferably used to prepare ABS resin applied to the field of household appliances.

[0039] In the present invention, grafting, coagulation, dehydration, and drying are performed on the prepared polybutadiene latex to obtain ABS rubber powder, and then blending and extrusion with SAN resin to obtain ABS resin are conventional techniques in the art. Those skilled in the art can perform combined screening according to actual needs, and the present invention will not be elaborated further.

[0040] Compared with the prior art, the beneficial effects of the technical solution of the present invention are as follows:

[0041] The present invention fully and effectively protects the double bonds of PB, preventing the aging and yellowing of the rubber powder from the root. The ABS resin prepared therefrom has excellent antioxidant properties, while reducing the b* value of the resin (<9), maintaining its impact resistance (reaching 270 J / m), tensile strength (reaching 64 MPa), and flexural strength (reaching 45 MPa). BRIEF DESCRIPTION OF THE DRAWINGS

[0042] Figure 1 TEM image of the polybutadiene latex provided in Example 1;

[0043] Figure 2 TEM image of the polybutadiene latex with an antioxidant layer prepared in Example 1;

[0044] Figure 3 It is a schematic diagram of the structure of ABS latex;

[0045] Figure 4 This is the H NMR spectrum of 3,5-dipropenyl-2,6-di-tert-butyl-4-methylphenol;

[0046] Figure 5 This is the H NMR spectrum of 3-isoprene-6-tert-butyl-2,5-dimethylphenol;

[0047] Figure 6 This is the H NMR spectrum of 5-butadiene-2-tert-butylphenol;

[0048] Figure 7 It is the H NMR spectrum of 3-isoprene-2-butyl-6-tert-butyl-4-methyl-5-butenylphenol;

[0049] Figure 8 This is the H NMR spectrum of 2,6-di-tert-butyl-4-methyl-3-allyl-5-propylphenol. DETAILED DESCRIPTION

[0050] In order to better understand the technical solution of the present invention, the content of the present invention is further described below in conjunction with the embodiments, but the content of the present invention is not limited to the following embodiments.

[0051] Unless otherwise specified, the raw materials used in the following examples and comparative examples of the present invention are obtained from commercial channels.

[0052] Potassium oleate, BM-400, was purchased from Ino Reagent;

[0053] Hydrogen peroxide, 80%, purchased from Aladdin;

[0054] Ferrous sulfate, 99%, purchased from Xilong Chemical;

[0055] Potassium persulfate, 99%, purchased from Xilong Chemical;

[0056] Acrylonitrile, 99%, purchased from Aladdin;

[0057] Styrene, 99%, purchased from Aladdin;

[0058] Potassium carbonate, 99%, purchased from Aladdin;

[0059] Cardanol, industrial product, Shanghai Jing Chemical Technology Co., Ltd.;

[0060] Tert-butyl chloride, analytical grade, from Sinopharm Chemical Reagent Co., Ltd.

[0061] The following test method is used in the embodiments of the present invention:

[0062] Latex particle size: The latex was diluted 20,000 times with deionized water, and the particle size was measured using a Malvern Zetasizer Nano-ZS90 particle size analyzer.

[0063] Transmission electron microscope image: 2% phosphotungstic acid was used to dye the diluted PB and ABS latex, and then dropped onto a copper grid. After drying under infrared light, the structure of the polymer was observed. Transmission electron microscope (TEM) manufacturer: Thermo Fisher, model: Talos F200c.

[0064] Nuclear magnetic spectrum: 400MHZ nuclear magnetic resonance spectrometer (NMR) was used for testing. Instrument manufacturer: Bruker, instrument model: AVANCEⅢ400M nuclear magnetic resonance spectrometer, reagent: CDCl 3 .

[0065] Yellowness index: standard ASTM E313-15e1, using American Hunterlab VIS instrument.

[0066] Mechanical properties: Tensile standard ASTM D638, using American INSTRON 5966; bending standard ASTM D790, using Xinsansi UTM4104X; Izod notched impact standard ASTM D256, 23°C, using Italian CEAST 9050.

[0067] Preparation of 3,5-dipropylene-2,6-di-tert-butyl-4-methylphenol antioxidant:

[0068] 100g of cardanol and 3g of catalyst were placed in a 200ml autoclave, the autoclave was sealed, hydrogen was introduced to 18MPaG, stirring was started, the heating temperature was 420℃, and the reaction was carried out for 8 hours. After the reaction was completed, the temperature was lowered to 60℃, the reaction mixture was taken out, and vacuum distillation was carried out at 100Pa and 160℃ for 1h, and meta-substituted C3-C15 olefin phenol was obtained after cooling.

[0069] Dissolve 30 g of the above product in 100 ml of cyclohexane. After complete dissolution, transfer it to a 250-ml three-neck reaction flask. Add 1.5 g of zinc chloride catalyst, start stirring, and heat to maintain the reaction temperature at 50 °C. Slowly add 9.5 g of tert-butyl chloride dropwise to the reaction flask. After the addition is complete, continue the reaction for 5 hours. After the reaction is completed, cool down the reaction mixture. Filter the reaction product and wash it with 5% KOH solution for alkaline washing, then wash it with distilled water until neutral. Under the conditions of 1000 PaG and 120 °C, perform vacuum distillation for 1 h to remove the solvent, water, and unreacted raw materials. After cooling, an antioxidant is obtained.

[0070] The following products were prepared using the above preparation route: 3,5-diallyl-2,6-di-tert-butyl-4-methylphenol, 3-isoprene-6-tert-butyl-2,5-dimethylphenol, 5-butadiene-2-tert-butylphenol, 3-isoprene-2-butyl-6-tert-butyl-4-methyl-5-butenylphenol, 2,6-di-tert-butyl-4-methyl-3-allyl-5-propylphenol. The product characterization results are shown in the appendix Figure 3-8 。

[0071] Example 1

[0072] Add 8 Kg of 300-nm polybutadiene latex and 4 Kg of deionized water to the reactor and start stirring. Heat the reactor to 65 °C. Add 500 g of 3,5-diallyl-2,6-di-tert-butyl-4-methylphenol antioxidant, 500 g of potassium oleate, 50 g of potassium carbonate, 100 g of potassium persulfate, and 7 Kg of deionized water to the emulsifying flask, and stir the mixture for emulsification. Continuously add the mixture dropwise to the reactor for 3 h, then heat to 75 °C and keep the temperature for 1 h to obtain polybutadiene latex. Put 10 g of ferrous sulfate into the reactor, and add 60 g of potassium oleate, 30 g of cumene hydroperoxide, 4 Kg of styrene, and 1.5 Kg of acrylonitrile dropwise to the reactor over 3 h. Heat to 80 °C and keep the temperature for 2 h. Then cool the reactor to 25 °C and filter to obtain ABS latex.

[0073] Example 2

[0074] Add 10 Kg of 250-nm polybutadiene latex and 5 Kg of deionized water to a reactor and start stirring. Heat the reactor to 75 °C. Add 1 Kg of 3-isoprene-6-tert-butyl-2,5-dimethylphenol antioxidant, 1 Kg of sodium dodecylbenzenesulfonate, 300 g of sodium bicarbonate, 300 g of sodium persulfate, and 8 Kg of deionized water to an emulsifying flask, and stir the mixture to emulsify it. Continuously add and react dropwise to the reactor for 4 h, then heat to 90 °C and keep warm for 1.5 h to obtain polybutadiene latex. Put 50 g of ferrous sulfate and 50 g of glucose into the reactor, and add dropwise 50 g of sodium dioctylsulfosuccinate, 10 g of ammonium persulfate, 8 Kg of styrene, and 3 Kg of acrylonitrile to the reactor over 2 h. Keep warm for 0.5 h, then cool the reactor to 25 °C and filter to obtain ABS latex.

[0075] Example 3

[0076] Add 6 Kg of 350-nm polybutadiene latex and 3 Kg of deionized water to a reactor and start stirring. Heat the reactor to 60 °C. Add 200 g of 5-butadiene-2-tert-butylphenol antioxidant, 300 g of disproportionated rosin potassium salt, 10 g of potassium bicarbonate, 10 g of potassium persulfate, and 6 Kg of deionized water to an emulsifying flask, and stir the mixture to emulsify it. Continuously add and react dropwise to the reactor for 2 h, then heat to 70 °C and keep warm for 0.5 h to obtain butadiene latex. Put 10 g of ferrous sulfate, 30 g of ethylenediaminetetraacetic acid sodium salt, and 40 g of sodium formaldehyde sulfoxylate into the reactor, and add dropwise 300 g of sodium dodecylsulfate, 50 g of diisopropylbenzene hydroperoxide, 3 Kg of styrene, and 1 Kg of acrylonitrile to the reactor over 5 h. Keep warm for 3 h, then cool the reactor to 25 °C and filter to obtain ABS latex.

[0077] Example 4

[0078] Add 7 Kg of 400-nm polybutadiene latex and 3.5 Kg of deionized water to a reactor and start stirring. Heat the reactor to 80 °C. Add 800 g of 3-isoprene-2-butyl-6-tert-butyl-4-methyl-5-butenylphenol antioxidant, 600 g of sodium dodecylsulfate, 100 g of sodium carbonate, 200 g of cumene hydroperoxide, and 7 Kg of deionized water to an emulsifying flask, and stir the mixture to emulsify it. Continuously add and react dropwise to the reactor for 3 h, then heat to 80 °C and keep warm for 5 h to obtain butadiene latex. Put 10 g of ferrous sulfate and 10 g of glucose into the reactor, and add dropwise 1 part by mass of disproportionated rosin potassium salt, 25 g of potassium persulfate, 5 Kg of styrene, and 2 Kg of acrylonitrile to the reactor over 4 h. Heat to 85 °C and keep warm for 1 h, then cool the reactor to 25 °C and filter to obtain ABS latex.

[0079] Comparative Example 1

[0080] Compared with Example 1, the difference is that instead of grafting the antioxidant of 3,5-diallyl-2,6-di-tert-butyl-4-methylphenol on the outer layer of PB latex, it is physically blended with PBA latex. Other conditions are the same as in Example 1.

[0081] Comparative Example 2

[0082] Compared with Example 1, the difference is that instead of grafting the antioxidant of 3,5-diallyl-2,6-di-tert-butyl-4-methylphenol on the outer layer of PB latex, it is replaced by grafting the antioxidant of 2,6-di-tert-butyl-4-methyl-3-allyl-5-propylphenol on the outer layer of PB. Other conditions are the same as in Example 1.

[0083] Comparative Example 3

[0084] Compared with Example 1, the difference is that instead of grafting the antioxidant of 3,5-diallyl-2,6-di-tert-butyl-4-methylphenol on the outer layer of PB latex, it is replaced by grafting the antioxidant of 3,5-diallyl-2,6-di-tert-butyl-4-methylphenol on the outer layer of ABS latex. Other conditions are the same as in Example 1.

[0085] According to the following steps, the ABS latex prepared in the examples and comparative examples was prepared into ABS rubber powder, and then blended and extruded with SAN resin to be injection molded into test specimens for testing:

[0086] 1) Preparation of ABS rubber powder

[0087] Add 2 kg of MgSO 4 , 200 kg of deionized water into the coagulation kettle and start stirring to fully dissolve MgSO 4 . Heat the coagulation kettle to 75 °C, and continuously feed 100 kg of the ABS graft latex prepared in step 1) into the coagulation kettle. The continuous feeding time is 1 hour. After the feeding is completed, heat the coagulation kettle to 90 °C and keep it warm for 1 hour. Then cool the coagulation kettle to room temperature, filter, wash, and dehydrate the coagulated slurry to obtain wet ABS rubber powder. Dry the wet ABS rubber powder in a fluidized bed dryer at 65 °C until the water content is <1% to obtain ABS rubber powder.

[0088] 2) Preparation, injection molding and performance testing of ABS resin

[0089] Using a twin-screw extruder, the three-section temperatures are 190 °C, 210 °C and 220 °C respectively. Using SAN resin with the LG Chemical brand SA 30 as the blending continuous phase and the ABS rubber powder prepared in step 2) as the blending dispersed phase, blend and extrude according to 18% of the polybutadiene rubber content respectively, and granulate to obtain ABS resin.

[0090] Prepare various test specimens of the above ABS resin on an injection molding machine at 210 °C, and test the b value, impact strength, tensile strength, and flexural strength of the ABS resin according to the ASTM D1925, ASTM D256, ASTM D638-2000, and ASTM D790-2000 standards respectively.

[0091] Table 1 Particle sizes of the prepared antioxidant-grafted PB latex and ABS latex

[0092] Particle size of antioxidant-grafted PB latex nm Particle size of ABS latex nm Example 1 308 360 Example 2 260 325 Example 3 355 420 Example 4 415 510 Comparative Example 1 300 350 Comparative Example 2 308 330 Comparative Example 3 300 355

[0093] Table 2 Whiteness and mechanical property test results of the ABS rubber powder prepared in the examples and comparative examples

[0094] b* value Tensile strength Mpa Flexural strength MPa Impact strength J / m Example 1 7.2 67.4 46.2 274 Example 2 7.6 66.5 45.3 270 Example 3 8.1 64.1 47.9 282 Example 4 7.9 66.4 47.4 277 Comparative Example 1 13.2 60.5 42.6 220 Comparative Example 2 12.8 55.3 40.5 205 Comparative Example 3 9.5 61.5 43.7 226

[0095] It can be seen from the test results of Examples 1-4 and Comparative Examples 1-3 that the ABS resin prepared using the polybutadiene latex prepared in the present invention has better mechanical properties and a lower b* value (both less than 9) compared to the ABS resin prepared using the polybutadiene latex prepared in the comparative examples.

[0096] Obviously, the above examples are only for clear illustration and not a limitation of the implementation manner. For those of ordinary skill in the art, other different forms of changes or modifications can be made based on the above description. It is not necessary and impossible to list all implementation manners here. And the obvious changes or modifications derived therefrom are still within the protection scope of the present invention.

Claims

1. A preparation method of a multi-layer structured ABS latex, characterized in that, the method grafts a hindered phenol antioxidant containing two unsaturated double bonds on the surface of a polybutadiene rubber core layer to form a functional layer, and then grafts styrene and acrylonitrile on the surface of the functional layer to prepare a multi-layer structured ABS latex.

2. The preparation method according to claim 1, characterized in that, the method comprises the following steps: S1: Add polybutadiene latex and water into a reactor, mix and keep warm; S2: Stir and emulsify the hindered phenol antioxidant, emulsifier, electrolyte, initiator and water; S3: Add the emulsion of S2 into the reactor of S1 for reaction, keep warm, and prepare polybutadiene latex; S4: Add a reducing agent into the reactor of S3, add an emulsifier, an initiator, styrene and acrylonitrile, keep warm, and prepare a multi-layer structured ABS latex.

3. The preparation method according to claim 1 or 2, characterized in that, in S1, 60-100 parts by weight of polybutadiene latex and 30-50 parts by weight of water; and / or, the particle size of the polybutadiene latex in S1 is 200-400 nm, preferably 250-350 nm; and / or, the heat preservation temperature in S1 is 60°C - 80°C.

4. The preparation method according to any one of claims 1-3, characterized in that, in S2, 2-10 parts by weight of hindered phenol antioxidant, 3-10 parts by weight of emulsifier, 0.1-3 parts by weight of electrolyte, 0.1-3 parts by weight of initiator, and 60-80 parts by weight of water; and / or, the hindered phenol antioxidant in S2 has the structure shown in formula (1); In formula (1), group R 1 , R 3 , R 5 are each independently selected from any one of hydrogen, C 1-10 linear, C 1-10 branched alkyl; groups R 2 , R 4 are each independently selected from hydrogen, C 1-6 linear hydrocarbon group, C 1-6 branched hydrocarbon group, C 3-6 isomerized hydrocarbon group, and there are two unsaturated carbon-carbon double bonds in groups R 2 , R 4 ; and / or, the emulsifier in S2 is an anionic emulsifier, preferably one or more of potassium oleate, potassium disproportionated rosin, sodium dodecyl sulfate, sodium dodecyl benzene sulfonate and sodium dioctyl sulfosuccinate; and / or, the electrolyte in S2 is an inorganic salt, preferably one or more of potassium bicarbonate, potassium carbonate, sodium bicarbonate, sodium carbonate, sodium tripolyphosphate; and / or, the initiator in S2 is selected from inorganic peroxides and / or organic peroxides, preferably one or more of potassium persulfate, sodium persulfate, ammonium persulfate, dicumyl peroxide, cumene hydroperoxide.

5. The preparation method according to any one of claims 1-4, characterized in that, the addition method of the emulsion in S3 is dropwise addition; preferably, the dropping time is 2-4 h; and / or, the heat preservation temperature in S3 is 70-90°C, and the heat preservation time is 0.5-5 h.

6. The preparation method according to any one of claims 1-5, characterized in that, in S4, 0.1-1 part by weight of reducing agent, 0.5-3 parts by weight of emulsifier, 0.1-0.5 part by weight of initiator, 30-80 parts by weight of styrene, 10-30 parts by weight of acrylonitrile; and / or, the reducing agent in S4 is one or more of ferrous sulfate, glucose, sodium pyrophosphate, ethylenediaminetetraacetic acid tetrasodium, sodium formaldehyde sulfoxylate; and / or, the emulsifier in S4 is an anionic emulsifier, preferably one or more of potassium oleate, potassium disproportionated rosin, sodium dodecyl sulfate, sodium dodecyl benzene sulfonate and sodium dioctyl sulfosuccinate; And / or, the initiator in S4 is selected from inorganic peroxides and / or organic peroxides, preferably one or more of potassium persulfate, sodium persulfate, ammonium persulfate, dicumyl peroxide, and cumene hydroperoxide; And / or, the emulsifier, initiator, styrene, and acrylonitrile in S4 are added by dropping; Preferably, the dropping time is 2 - 5 h; And / or, the heat preservation temperature in S4 is 70 - 90 °C, and the heat preservation time is 0.5 - 3 h.

7. A multi-layered ABS latex, the latex is prepared by the preparation method according to any one of claims 1 - 6, characterized in that, the latex has a multi-layered structure; Preferably, in the multi-layered latex, a hindered phenol antioxidant functional layer containing two unsaturated double bonds is grafted on the surface of the polybutadiene rubber core layer, and styrene and acrylonitrile are grafted on the surface of the functional layer.

8. A polybutadiene latex, the latex is obtained by the preparation method according to any one of claims 2 - 5, characterized in that, a hindered phenol antioxidant functional layer containing two unsaturated double bonds is grafted on the surface of the polybutadiene rubber core layer in the latex.

9. The use of a multi-layered ABS latex, the latex is the latex obtained by the preparation method according to any one of claims 1 - 6, or the latex according to claim 7, characterized in that, the latex is used for preparing ABS resins applied to the fields of household appliances, office supplies, and automobiles, preferably for preparing ABS resins applied to the field of household appliances.

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