A MABS graft copolymer resin, a method of making and a transparent MABS resin composition

Abstract

The present application provides a kind of MABS graft copolymer resin, preparation method and transparent MABS resin composition.MABS graft copolymer resin is prepared from the raw materials comprising the following parts by mass: polybutadiene rubber latex 50-70 parts, alkyl acrylate monomer 25-35 parts, styrene monomer 10-15 parts, acrylonitrile monomer 1-10 parts;Wherein, the average particle size of the polybutadiene rubber latex is 260-300nm, particle size distribution (PDI)≤0.15, and the content ratio of particle size greater than or equal to 800nm is not higher than 10wt%, the transparent MABS resin composition prepared from the polybutadiene latex has excellent transparency and impact resistance transparent ABS graft copolymer resin and transparent ABS resin composition.

Description

Technical Field

[0001] This invention belongs to the field of polymers, specifically relating to an acrylonitrile-butadiene-styrene-methyl methacrylate (MABS) graft copolymer resin, its preparation method, and a transparent MABS resin composition. Background Technology

[0002] As consumers increasingly demand higher quality of life, the fields where ABS resin is widely used, such as home appliances, automobiles, communication equipment, and computers, are gradually requiring ABS materials to possess both excellent intrinsic properties and good appearance. For example, in recent years, industrial development and significant product differentiation have led to substantial changes in product design. Transparent designs have attracted considerable attention. These design changes necessitate changes in raw materials. Therefore, extensive research on transparent materials is actively underway.

[0003] For this reason, various techniques have been developed to impart transparency to acrylonitrile-butadiene-styrene (ABS) resin by introducing alkyl acrylate or alkyl methacrylate monomers into ABS resin. Patent CN1297580C describes a transparent acrylonitrile-butadiene-styrene copolymer resin with good chemical resistance and transparency, obtained by graft copolymerization on a) conjugated diene latex; b) alkyl methacrylate or alkyl acrylate compounds; c) aromatic ethylene compounds; and d) acrylonitrile compounds, as well as its preparation method. The resin obtained by this method generally has poor optical properties, with haze values ​​all above 2.1. Patent CN101072803B describes a method for preparing a transparent styrene-acrylonitrile-acrylate terpolymer resin and the transparent styrene-acrylonitrile-acrylate terpolymer resin prepared by this method. This transparent resin is easily molded due to its good flowability, can be mixed with various other compounds due to its good chemical resistance, and hardly fades due to its good fading resistance. However, the transparent ABS resin obtained by this method has poor impact strength, limiting its application scenarios.

[0004] Therefore, researching and preparing transparent ABS resin compositions that simultaneously possess high transparency and high impact resistance is of great practical significance. Summary of the Invention

[0005] Therefore, in view of the above-mentioned problems existing in the prior art, the present invention has been made. One object of the present invention is to provide a MABS graft copolymer resin and a method for preparing it, particularly by controlling the mass proportion of large particles of polybutadiene rubber particles in the MABS graft copolymer resin, while obtaining a specified rubber particle size and particle size distribution index.

[0006] Another object of the present invention is to provide a transparent MABS resin composition by incorporating the above-mentioned MABS graft copolymer resin, thereby obtaining a transparent MABS resin composition with high transparency and impact resistance.

[0007] To achieve the above technical effects, the present invention adopts the following technical solution:

[0008] According to one aspect of the present invention, a MABS graft copolymer resin is provided, which is prepared from raw materials comprising the following parts by weight:

[0009] 50-70 parts of polybutadiene rubber latex

[0010] 25-35 parts of alkyl acrylate monomers,

[0011] 10-15 parts of styrene monomers

[0012] Acrylonitrile monomers: 1-10 parts;

[0013] The polybutadiene rubber latex has an average particle size of 260-300 nm and a particle size distribution of...

[0014] (PDI)≤0.15, and the content of particles with a diameter greater than or equal to 800nm ​​does not exceed 10wt%.

[0015] Specifically, the raw material mass percentage of the MABS graft copolymer resin is given as follows:

[0016] Polybutadiene rubber latex is available in quantities of 50 parts by weight, 52 parts by weight, 55 parts by weight, and 58 parts by weight.

[0017] 60 parts by weight, 62 parts by weight, 65 parts by weight, 68 parts by weight, 70 parts by weight, etc.

[0018] The alkyl acrylate monomers can be in quantities of 25 parts by weight, 27 parts by weight, 30 parts by weight, 32 parts by weight, 33 parts by weight, 35 parts by weight, etc.

[0019] Styrene monomers can be in quantities of 10 parts by weight, 11 parts by weight, 12 parts by weight, 13 parts by weight, 14 parts by weight, 15 parts by weight, etc.

[0020] Acrylonitrile monomers can be in quantities of 1 part by weight, 3 parts by weight, 5 parts by weight, 7 parts by weight, 9 parts by weight, 10 parts by weight, etc.

[0021] Specifically, in the MABS graft copolymer resin, the average particle size of the polybutadiene rubber latex can be 260nm, 270nm, 280nm, 290nm, 300nm, etc.

[0022] Particle size distribution (PDI) can be 0.15, 0.14, 0.13, 0.12, 0.11, 0.10,

[0023] 0.08, 0.05, 0.03, etc.;

[0024] The content percentage of particles with a diameter greater than or equal to 800 nm can be 10 wt%, 9 wt%, 8 wt%, 7 wt%, etc.

[0025] 6wt%, 5wt%, 4wt%, 3wt%, 2wt%, 1wt%, etc.

[0026] In one embodiment of the present invention, the alkyl acrylate monomer is one or more selected from methyl methacrylate, ethyl methacrylate, propyl methacrylate, 2-ethylhexyl methacrylate, decyl methacrylate and lauryl methacrylate.

[0027] In one embodiment of the present invention, the styrene monomer is one or more selected from styrene, α-methylstyrene, p-methylstyrene and vinyltoluene.

[0028] In one embodiment of the present invention, the acrylonitrile monomer is one or more selected from acrylonitrile, methacrylonitrile and ethyl acrylonitrile.

[0029] In one embodiment of the present invention, the polybutadiene rubber latex is a butadiene homopolymer rubber latex.

[0030] According to another aspect of the present invention, a method for preparing the MABS graft copolymer resin is provided, the method comprising the following steps:

[0031] S1: Add 70-110 parts by weight (preferably 80-100 parts by weight) of deionized water, 1-5 parts by weight (preferably 2-4 parts by weight) of electrolyte, 1-5 parts by weight (preferably 2-4 parts by weight) of emulsifier (1), 0.1-3 parts by weight (preferably 0.2-2 parts by weight) of molecular weight control agent (1), 60-80 parts by weight (preferably 65-75 parts by weight) of butadiene and 0.1-3 parts by weight (preferably 0.2-2 parts by weight) of initiator (1) to the reactor, start stirring and heat the reactor to 65-85°C (preferably 70-80°C);

[0032] When the butadiene conversion rate is 20-30% (preferably 22-28%), add 10-30 parts by mass (preferably 12-20 parts by mass) of butadiene and continue the reaction;

[0033] When the butadiene conversion rate is 50-60% (preferably 52-58%), add 10-30 parts by weight (preferably 12-20 parts by weight) of butadiene and 0.1-3 parts by weight (preferably 0.2-2 parts by weight) of initiator (2) and continue the reaction;

[0034] When the butadiene conversion rate is 70-80% (preferably 72-78%), add 0.1-2 parts by weight (preferably 0.2-1.8 parts by weight) of emulsifier (2) and 0.1-3 parts by weight (preferably 0.2-2 parts by weight) of initiator (3) and continue the reaction;

[0035] When the butadiene conversion rate reaches ≥86% (preferably ≥88%), the reaction is stopped by cooling to obtain polybutadiene rubber latex;

[0036] S2: 25-50 parts by weight (preferably 30-45 parts by weight) of deionized water, 25-35 parts by weight (preferably 27-33 parts by weight) of alkyl acrylate monomers, 10-15 parts by weight (preferably 11-14 parts by weight) of styrene monomers, and 1-10 parts by weight (preferably 2-8 parts by weight) of acrylonitrile monomers, along with 0.001-0.1 parts by weight (preferably 0.002-0.08 parts by weight) of reducing agent, 0.01-1 parts by weight (preferably 0.02-0.8 parts by weight) of complexing agent, 0.01-1 parts by weight (preferably 0.02-0.8 parts by weight) of co-reducing agent, and 0.5-5 parts by weight (preferably 0.6-3 parts by weight) of emulsifier (3... 0.1-3 parts by weight (preferably 0.2-2 parts by weight) of molecular weight control agent (2) and 0.01-0.3 parts by weight (preferably 0.02-0.29 parts by weight) of initiator (4) are continuously added to 50-70 parts by weight (preferably 55-65 parts by weight) of polybutadiene rubber latex prepared in step S1, so that these monomers are grafted and polymerized. The continuous feeding time is 3-6 hours (preferably 3.5-5.5 hours), and the temperature is controlled at 50-65℃ (preferably 55-60℃) during continuous feeding. After feeding is completed, the temperature is raised to 65-80℃ (preferably 68-75℃) and cured for another 1-3 hours (preferably 1.5-2.5 hours) to obtain MABS graft copolymer resin.

[0037] In one embodiment of the invention, step S1 is performed under a nitrogen atmosphere.

[0038] In one embodiment of the present invention, the emulsifiers (1), (2), and (3) are selected from one or more of potassium oleate, potassium rosinate, sodium dodecyl sulfate, sodium dodecylbenzene sulfonate, sodium dodecyl allyl sulfosuccinate, dipotassium C16-C18 alkenyl succinate, and dioctyl sodium sulfosuccinate.

[0039] In one embodiment of the present invention, the initiators (1), (2), and (3) are one or more water-soluble initiators selected from potassium persulfate, sodium persulfate, ammonium persulfate, and hydrogen peroxide.

[0040] In one embodiment of the present invention, the initiator (4) is one or more oil-soluble initiators selected from dicumyl hydroperoxide, tert-hexyl hydroperoxide, dicumyl hydroperoxide, tert-butyl hydroperoxide, methyl ethyl ketone peroxide, methyl isobutyl ketone peroxide, cyclohexanone peroxide, cumyl hydroperoxide, tert-butyl hydroperoxide, benzoyl peroxide, lauroyl peroxide, tert-butyl peroxide, tert-butyl peroxybenzoate, tert-butyl peroxy2-ethylhexanoate, and bis(4-tert-butylcyclohexyl)dicarbonate peroxide.

[0041] In one embodiment of the present invention, the electrolyte is one or more of potassium carbonate, sodium carbonate, potassium bicarbonate, sodium bicarbonate, sodium phosphate, sodium pyrophosphate, potassium pyrophosphate, and sodium tripolyphosphate.

[0042] In one embodiment of the present invention, the molecular weight control agents (1) and (2) are C8-C14 alkyl thiols, selected from one or more of tert-dodecyl thiols, n-dodecyl thiols, n-octyl thiols, tert-octyl thiols, sec-octyl thiols, and tert-octyl thiols.

[0043] In one embodiment of the present invention, the reducing agent is one or both of ferrous sulfate and ferrous chloride.

[0044] In one embodiment of the present invention, the complexing agent is one or more of the following: trisodium triamcinolone, disodium ethylenediaminetetraacetate, tetrasodium ethylenediaminetetraacetate, sodium pyrophosphate, and sodium hexametaphosphate.

[0045] In one embodiment of the present invention, the reducing agent is one or more of sodium dithionite, sodium formaldehyde sulfoxylate, isoascorbic acid, glucose, and lactose.

[0046] The MABS graft copolymer resin prepared by the method in step S2 of the present invention exhibits the characteristics of a latex and can be recycled into powder through processes such as coagulation, dehydration, and drying. For coagulation, salts of, for example, calcium chloride, magnesium sulfate, or aluminum sulfate; or acidic compounds of, for example, sulfuric acid, nitric acid, or hydrochloric acid, or mixtures thereof, can be used as coagulants, added in the mass ratios commonly used in the art. These processes are all conventional operating methods in the field, and the operating conditions and parameters used can be obtained by those skilled in the art based on existing technology. The present invention does not make specific requirements and will not elaborate further here.

[0047] According to another aspect of the present invention, a transparent MABS resin composition is provided, comprising the above-described MABS graft copolymer resin and methyl methacrylate-styrene-acrylonitrile (MSAN) resin;

[0048] The MABS graft copolymer resin is present in the transparent MABS resin composition at a content of 5-30 wt%, preferably 15-25 wt%, and more preferably 20-25 wt%.

[0049] The MSAN resin described in this invention is a product already disclosed in the prior art. It can be a commercially available product that can be purchased through commercial channels, or it can be prepared by itself using existing processes. This invention does not have any special requirements regarding its source.

[0050] In one embodiment of the present invention, the MSAN resin is a resin prepared by polymerizing 0-75 parts by weight of alkyl methacrylate monomers, 10-50 parts by weight of styrene monomers and 10-20 parts by weight of acrylonitrile monomers.

[0051] Specifically, the polymerization reaction can be a conventional polymerization method used in the field, such as bulk polymerization, solution polymerization, suspension polymerization, etc. The equipment used, specific operating conditions and selected operating parameters can be obtained by those skilled in the art with reference to the prior art, and there are no special requirements in this invention.

[0052] Depending on its intended use, the transparent MABS resin composition may also contain one or more additives selected from lubricants, antioxidants, antistatic agents, mold release agents, and UV stabilizers. These additives are conventional auxiliaries and can be selected from those commonly used in the field. For example, the lubricant may be selected from ethylene bis-stearamide, polyethylene oxide wax, metal stearates, and various silicone oils, and the amount of lubricant used based on 100 parts by weight of the transparent MABS resin composition may be 0-5 parts by weight, preferably 0.1-2 parts by weight.

[0053] The transparent MABS resin composition can be kneaded to provide a thermoplastic transparent MABS resin. More specifically, the transparent MABS resin composition is uniformly dispersed using a single-screw extruder or a twin-screw extruder. The dispersed composition is passed through a water bath and then cut and dried to obtain granular thermoplastic transparent MABS resin.

[0054] According to another aspect of the present invention, a thermoplastic transparent MABS resin is provided, which is prepared by extrusion and injection molding of the above-mentioned transparent MABS resin composition.

[0055] Specifically, the thermoplastic transparent MABS resin of the present invention has a light transmittance of 91.0 or higher and a haze value of 1.8 or lower when measured on a 3mm thick sheet at room temperature according to ASTM D1003.

[0056] The impact strength of the cantilever beam, measured at 1 / 4" according to ASTM D256, is 16 kJ / m. 2 above.

[0057] Compared with the prior art, the beneficial effects of the present invention are as follows:

[0058] This invention provides a MABS graft copolymer resin and a transparent MABS resin composition. By controlling the volume ratio of large particles of polybutadiene rubber particles in the MABS graft copolymer resin, and simultaneously obtaining a specified rubber particle size and particle size distribution index, a transparent MABS resin composition with high transparency and impact resistance is obtained.

[0059] Specific implementation methods

[0060] To better understand the technical solution of the present invention, the following embodiments further illustrate the content of the present invention, but the content of the present invention is not limited to the following embodiments.

[0061] Unless otherwise specified, the raw materials used in the following embodiments and comparative examples of this invention are obtained from ordinary commercial channels.

[0062] Examples 1-5

[0063] Based on the types and amounts of raw materials and experimental conditions in Table 1, prepare polybutadiene rubber latex (A-1 to A-5) according to the following steps:

[0064] Under a nitrogen atmosphere, add 70-110g of deionized water, 1-5g of electrolyte, 1-5g of emulsifier (1), 0.1-3g of molecular weight control agent (1), 60-80g of butadiene (A) and 0.1-3g of initiator (1) to the reactor, start stirring and heat the reactor to the reaction temperature of 65-85℃;

[0065] When the butadiene conversion rate (1) is 20-30%, add 10-30g of butadiene (B) and continue the reaction;

[0066] When the butadiene conversion rate (2) is 50-60%, add 10-30g of butadiene (C) and 0.1-3g of initiator (2) and continue the reaction;

[0067] When the butadiene conversion rate (3) is 70-80%, add 0.1-2g of emulsifier (2) and 0.1-3g of initiator (3) and continue the reaction;

[0068] When the butadiene conversion rate (4) reaches ≥86%, the reaction is stopped by cooling to obtain polybutadiene rubber latex.

[0069] Table 1 Formulations and reaction conditions for Examples 1-5

[0070]

[0071]

[0072] Comparative Example 1

[0073] Preparation of polybutadiene rubber latex (a-1):

[0074] The process of Example 1 was repeated, except that all materials added during the reaction in Example 1 were added to the reactor all at once before the reaction started, and then the reaction was carried out at the reaction temperature of Example 1. After reaching the conversion rate of Example 1, the temperature was lowered and the reaction was stopped to obtain polybutadiene rubber latex a-1.

[0075] Comparative Example 2

[0076] Preparation of polybutadiene rubber latex (a-2):

[0077] The process of Example 3 was repeated, except that the materials that reached the butadiene conversion rate (1) and butadiene conversion rate (2) were combined together and added together when the butadiene conversion rate reached 25.5%. The subsequent operation was the same as in Example 3. When the final butadiene conversion rate reached 90.6%, the reaction was stopped by cooling to obtain polybutadiene rubber latex a-2.

[0078] Comparative Example 3

[0079] Preparation of polybutadiene rubber latex (a-3):

[0080] Repeat the process of Example 5, except that the materials that reach the butadiene conversion rate (2) and butadiene conversion rate (3) are combined together and added together when the butadiene conversion rate reaches 57.0%. The subsequent operation is the same as in Example 5. When the final butadiene conversion rate reaches 92.6%, the reaction is stopped by cooling to obtain polybutadiene rubber latex a-3.

[0081] The average particle size and particle size distribution index of the polybutadiene rubber latexes prepared in Examples 1-5 and Comparative Examples 1-3, as well as the percentage of particles larger than 800 nm, were tested. The results are shown in Table 2.

[0082] The average particle size, particle size distribution, and percentage of particles larger than 800 nm in polybutadiene rubber latex were obtained by diluting the sample and then testing it using a Malvern nanoparticle size analyzer (Zetasizer Nano series): 1 g of latex sample filtered through a 100-mesh screen was added to 100 g of deionized water for thorough dilution, and then another 1 g of this diluted solution was added to 100 g of deionized water for further dilution. The average particle size of the latex was then measured using a Malvern nanoparticle size analyzer (Zetasizer Nano series).

[0083] Particle size distribution and the percentage of particles larger than 800 nm.

[0084] Butadiene conversion test method: Take 0.05g of sample into a 20ml headspace vial, dilute with DMF to 1.00g, and analyze the sample using gas chromatography to determine the residual butadiene monomer content. Calculate the butadiene conversion rate by substituting the test results into the following formula:

[0085]

[0086] Table 2. Test results of polybutadiene rubber latex prepared in the examples and comparative examples.

[0087]

[0088] As shown in Table 2, in the preparation examples 1-5 of the present invention, polybutadiene latex with an average particle size distribution of 260-300 nm, a particle size distribution (PDI) ≤ 0.15, and a content of particles with a particle size greater than or equal to 800 nm not exceeding 10 wt% can be obtained. However, the average particle size, particle size distribution, and content of polybutadiene latex prepared as comparative examples 1-3 do not meet the index range required by the present invention.

[0089] Using the polybutadiene latex prepared in Examples 1-5 and Comparative Examples 1-3, the MABS graft copolymer resins of Examples 6-10 and Comparative Examples 4-6 were prepared in the following manner.

[0090] Examples 6-10

[0091] Based on the types and amounts of raw materials and experimental conditions in Table 3, prepare MABS graft copolymer resins (A-6 to 10) according to the following steps:

[0092] 25-50g of deionized water, 25-35g of alkyl acrylate monomers, 10-15g of styrene monomers and 1-10g of acrylonitrile monomers, as well as 0.001-0.1g of reducing agent, 0.01-1g of complexing agent, 0.01-1g of co-reducing agent, 0.5-5g of emulsifier (3), 0.1-3g of molecular weight control agent (2) and 0.01-0.3g of initiator (4) are continuously added to 50-70g of polybutadiene rubber latex prepared in step S1 to allow these monomers to graft polymerize. The continuous feeding time is 3-6 hours, and the temperature is controlled at 50-65℃ during continuous feeding. After feeding is completed, the temperature is raised to 65-80℃ and the curing continues for 1-3 hours to obtain MABS graft copolymer resin.

[0093] Table 3 Formulations and reaction conditions for Examples 6-10

[0094]

[0095]

[0096] Comparative Example 4

[0097] Preparation of MABS graft copolymer resin a-4:

[0098] The process of Example 6 was repeated, except that the polybutadiene rubber latex A-1 prepared in Example 1 was replaced with an equal mass of polybutadiene rubber latex a-1 prepared in Comparative Example 1, while other operations and conditions remained unchanged.

[0099] Comparative Example 5

[0100] Preparation of MABS graft copolymer resin a-5:

[0101] The process of Example 6 was repeated, except that the polybutadiene rubber latex A-1 prepared in Example 1 was replaced with polybutadiene rubber latex a-2 prepared in Comparative Example 2 by an equal mass, while other operations and conditions remained unchanged.

[0102] Comparative Example 6

[0103] Preparation of MABS graft copolymer resin a-6:

[0104] The process of Example 6 was repeated, except that the polybutadiene rubber latex A-1 prepared in Example 1 was replaced with the polybutadiene rubber latex a-3 prepared in Comparative Example 3 by an equal mass, while other operations and conditions remained unchanged.

[0105] Add 2g H2SO4 and 200g deionized water to the coagulation vessel and start stirring to fully dissolve the H2SO4. Heat the coagulation vessel to 75°C and continuously feed 100g of MABS graft copolymer resin latex prepared in Examples 6-10 and Comparative Examples 4-6 into the coagulation vessel for 1 hour. After feeding, heat the coagulation vessel to 90°C and keep it at that temperature for 1 hour. Cool the coagulation vessel to room temperature and filter, wash, and dehydrate the coagulated slurry to obtain ABS wet rubber powder. Dry the ABS wet rubber powder in a fluidized bed dryer at 65°C until the water content is <1%, thus obtaining the MABS graft copolymer resin prepared in Examples 6-10 and Comparative Examples 4-6.

[0106] A twin-screw extruder was used at 200-220°C. LG Chem's MSAN resin (XT-500) was used as the continuous phase, and MABS graft copolymer resins prepared in Examples 6-10 and Comparative Examples 4-6 were used as the dispersed phase. The resins were blended, extruded, and granulated according to a polybutadiene rubber content of 15% to obtain thermoplastic transparent MABS resin.

[0107] Various test specimens were prepared using the above-mentioned MABS resin at 190°C on an injection molding machine. The light transmittance, haze, and cantilever beam notched impact strength of the thermoplastic transparent MABS resin were tested according to ASTM D1003 and ASTM D256, respectively. The results are shown in Table 3.

[0108] Table 3. Performance Comparison of Thermoplastic Transparent MABS Resin

[0109]

[0110] As can be seen from Table 3 above, unlike Comparative Examples 1-3, Examples 1-5 of the present invention, by controlling the mass proportion of large polybutadiene rubber particles in the MABS graft copolymer resin, simultaneously obtain a specified rubber particle size and particle size distribution index, thereby obtaining a transparent MABS resin composition with high transparency and impact resistance. Furthermore, it can be seen that the thermoplastic MABS resin prepared by Examples 1-5 has a light transmittance of 91.0 or higher, a haze value of 1.8 or lower, and a cantilever beam impact strength of 16 kJ / m². 2 above.

[0111] Obviously, the above embodiments are merely illustrative examples for clear explanation and are not intended to limit the implementation. Those skilled in the art will recognize that other variations or modifications can be made based on the above description. It is neither necessary nor possible to exhaustively list all possible implementations here. However, obvious variations or modifications derived therefrom are still within the scope of protection of this invention.

Claims

1. A graft copolymer resin, characterized in that, It is prepared from raw materials comprising the following parts by weight: 50-70 parts of polybutadiene rubber latex 25-35 parts of alkyl acrylate monomers, 10-15 parts of styrene monomers Acrylonitrile monomers: 1-10 parts; The polybutadiene rubber latex has an average particle size distribution of 260-300 nm, a particle size distribution (PDI) ≤ 0.15, and the content of particles with a particle size greater than or equal to 800 nm is not higher than 10 wt%. The method for preparing the graft copolymer resin includes the following steps: S1: Add 70-110 parts by weight of deionized water, 1-5 parts by weight of electrolyte, 1-5 parts by weight of emulsifier (1), 0.1-3 parts by weight of molecular weight control agent (1), 60-80 parts by weight of butadiene and 0.1-3 parts by weight of initiator (1) to the reactor, start stirring and heat the reactor to 65-85℃; When the butadiene conversion rate reaches 20-30%, add 10-30 parts by mass of butadiene and continue the reaction; When the butadiene conversion rate is 50-60%, add 10-30 parts by mass of butadiene and 0.1-3 parts by mass of initiator (2) and continue the reaction; When the butadiene conversion rate is 70-80%, add 0.1-2 parts by weight of emulsifier (2) and 0.1-3 parts by weight of initiator (3) and continue the reaction. When the butadiene conversion rate reaches ≥86%, cool down to end the reaction and obtain polybutadiene rubber latex. S2: 25-50 parts by weight of deionized water, 25-35 parts by weight of alkyl acrylate monomers, 10-15 parts by weight of styrene monomers and 1-10 parts by weight of acrylonitrile monomers, as well as 0.001-0.1 parts by weight of reducing agent, 0.01-1 parts by weight of complexing agent, 0.01-1 parts by weight of co-reducing agent, 0.5-5 parts by weight of emulsifier (3), 0.1-3 parts by weight of molecular weight control agent (2) and 0.01-0.3 parts by weight of initiator (4) are continuously added to 50-70 parts by weight of polybutadiene rubber latex prepared in step S1, so that these monomers are grafted and polymerized. The continuous feeding time is 3-6 hours, and the temperature is controlled at 50-65℃ during continuous feeding. After feeding is completed, the temperature is raised to 65-80℃ and the curing is continued for 1-3 hours to obtain graft copolymer resin.

2. The graft copolymer resin according to claim 1, characterized in that, The alkyl acrylate monomer is selected from one or more of methyl methacrylate, ethyl methacrylate, propyl methacrylate, 2-ethylhexyl methacrylate, decyl methacrylate and lauryl methacrylate.

3. The graft copolymer resin according to claim 1, characterized in that, The styrene monomer is selected from one or more of styrene, α-methylstyrene, p-methylstyrene, and vinyltoluene.

4. The graft copolymer resin according to claim 1, characterized in that, The acrylonitrile monomer is selected from one or more of acrylonitrile, methacrylonitrile, and ethyl acrylonitrile.

5. The graft copolymer resin according to claim 1, characterized in that, The polybutadiene rubber latex is a butadiene homopolymer rubber latex.

6. A method for preparing the graft copolymer resin according to any one of claims 1-5, characterized in that it comprises the following steps: S1: Add 70-110 parts by weight of deionized water, 1-5 parts by weight of electrolyte, 1-5 parts by weight of emulsifier (1), 0.1-3 parts by weight of molecular weight control agent (1), 60-80 parts by weight of butadiene and 0.1-3 parts by weight of initiator (1) to the reactor, start stirring and heat the reactor to 65-85℃; When the butadiene conversion rate reaches 20-30%, add 10-30 parts by mass of butadiene and continue the reaction; When the butadiene conversion rate is 50-60%, add 10-30 parts by mass of butadiene and 0.1-3 parts by mass of initiator (2) and continue the reaction; When the butadiene conversion rate is 70-80%, add 0.1-2 parts by weight of emulsifier (2) and 0.1-3 parts by weight of initiator (3) and continue the reaction. When the butadiene conversion rate reaches ≥86%, cool down to end the reaction and obtain polybutadiene rubber latex. S2: 25-50 parts by weight of deionized water, 25-35 parts by weight of alkyl acrylate monomers, 10-15 parts by weight of styrene monomers and 1-10 parts by weight of acrylonitrile monomers, as well as 0.001-0.1 parts by weight of reducing agent, 0.01-1 parts by weight of complexing agent, 0.01-1 parts by weight of co-reducing agent, 0.5-5 parts by weight of emulsifier (3), 0.1-3 parts by weight of molecular weight control agent (2) and 0.01-0.3 parts by weight of initiator (4) are continuously added to 50-70 parts by weight of polybutadiene rubber latex prepared in step S1, so that these monomers are grafted and polymerized. The continuous feeding time is 3-6 hours, and the temperature is controlled at 50-65℃ during continuous feeding. After feeding is completed, the temperature is raised to 65-80℃ and the curing is continued for 1-3 hours to obtain graft copolymer resin.

7. The preparation method according to claim 6, characterized in that, The emulsifiers (1), (2), and (3) are selected from one or more of potassium oleate, potassium rosinate, sodium dodecyl sulfate, sodium dodecylbenzene sulfonate, sodium dodecyl allyl sulfosuccinate, dipotassium C16-C18 alkenyl succinate, and dioctyl sodium sulfosuccinate; and / or The initiators (1), (2), and (3) are one or more water-soluble initiators selected from potassium persulfate, sodium persulfate, ammonium persulfate, and hydrogen peroxide; and / or The initiator (4) is one or more oil-soluble initiators selected from one or more of dicumyl hydroperoxide, tert-hexyl hydroperoxide, and tert-butyl cumyl hydroperoxide; and / or The electrolyte is one or more of potassium carbonate, sodium carbonate, potassium bicarbonate, sodium bicarbonate, sodium phosphate, sodium pyrophosphate, potassium pyrophosphate, and sodium tripolyphosphate; and / or The molecular weight control agents (1) and (2) are C8-C14 alkyl thiols, selected from one or more of tert-dodecyl thiols, n-dodecyl thiols, n-octyl thiols, tert-octyl thiols, tert-octyl thiols, and tert-octyl thiols. The reducing agent is one or both of ferrous sulfate and ferrous chloride; and / or The complexing agent is one or more of the following: trisodium aminetriacetate, disodium ethylenediaminetetraacetate, tetrasodium ethylenediaminetetraacetate, sodium pyrophosphate, and sodium hexametaphosphate, and / or The reducing agent is one or more of sodium dithionite, sodium formaldehyde sulfoxylate, isoascorbic acid, glucose, and lactose.

8. A transparent resin composition comprising the graft copolymer resin according to any one of claims 1-5 or the graft copolymer resin prepared by the method of claim 6 or 7 and MSAN resin; The content of the acrylonitrile-butadiene-styrene-methyl methacrylate graft copolymer resin in the transparent resin composition is 15-30 wt%.

9. The transparent resin composition according to claim 8, characterized in that, The content of the acrylonitrile-butadiene-styrene-methyl methacrylate graft copolymer resin in the transparent resin composition is 15-25 wt%.

10. The transparent resin composition according to claim 9, characterized in that, The content of the graft copolymer resin in the transparent resin composition is 20-25 wt%.

11. The transparent resin composition according to claim 8, characterized in that, The MSAN resin is a resin prepared by polymerizing 0-75 parts by weight (excluding 0 parts by weight) of alkyl methacrylate monomers, 10-50 parts by weight of styrene monomers and 10-20 parts by weight of acrylonitrile monomers.

12. A thermoplastic transparent resin, characterized in that, The transparent resin composition according to any one of claims 8-11 is prepared by extrusion and injection molding.

13. The thermoplastic transparent resin according to claim 12, characterized in that, According to ASTM D1003, the light transmittance measured at room temperature on a 3mm thick sheet is above 91.0, and the haze value is below 1.8; according to ASTM D256, the cantilever beam impact strength measured at 1 / 4" is 16kJ / m. 2 above.

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