A polymer agglomerating agent, its preparation method and use

Abstract

The application provides a high polymer agglomerating agent and a preparation method thereof. The high polymer agglomerating agent takes 1,3-butadiene as a main polymerization monomer, takes an alpha, beta-unsaturated acid as a copolymerization monomer, and takes an auxiliary agent including an emulsifier, an initiator and deionized water. The high polymer agglomerating agent is further used to prepare a large-particle-size polybutadiene latex and a polyacrylate latex, the components are simple, the introduction of more new monomers is reduced, the latex stability in the agglomeration process is improved, and then ABS and ASA resins are prepared, the impact resistance and tensile properties of the ABS and ASA resins are improved, and the impact resistance under low-temperature working conditions is improved in particular.

Description

Technical Field

[0001] This invention belongs to the field of engineering plastics ABS technology, and specifically relates to the preparation and application of an agglomerating agent in the preparation process of large particle size ABS. Background Technology

[0002] ABS resin is an acrylonitrile-butadiene-styrene copolymer, a high-strength, tough, and easily processed thermoplastic polymer with excellent moldability, primarily used in alloys and plastics. The synthesis methods for ABS resin are mainly divided into two types: continuous bulk synthesis and emulsion blending. The emulsion blending method is the most widely used technology for preparing ABS resin. The key to preparing ABS resin using the emulsion blending method lies in the preparation of ABS powder during the resin preparation process. Generally, ABS powder is mainly obtained by grafting large-particle-size polybutadiene latex.

[0003] The preparation methods for large-particle-size polybutadiene latex are divided into one-step and two-step methods. The one-step method for preparing large-particle-size polybutadiene latex originated from the JSR technology in Japan. It involves polymerizing butadiene monomers at high emulsifier concentrations using emulsion polymerization. During the process, monomers or emulsifiers are added to achieve a final polybutadiene latex particle size of 300 nm and a solid content as high as 50-60%. Its advantages include a narrow latex particle size distribution and good stability, but its disadvantages include a long preparation cycle and low efficiency.

[0004] The two-step process for preparing large-particle-size polybutadiene latex involves first preparing small-particle-size polybutadiene latex (particle size between 70-150 nm, preferably 90-110 nm), and then using agglomerating agents such as acetic acid, electrolytes, or high-pressure homogenization to agglomerate the small-particle-size polybutadiene latex into large-particle-size polybutadiene latex. The advantage of this process is its fast polymerization rate, with the entire polymerization process taking only 14-16 hours, half the time of the one-step method for preparing large-particle-size latex. However, its disadvantages are also quite prominent. For example, the wastewater generated after agglomeration with acetic acid or electrolytes contains a large amount of salt, increasing wastewater treatment costs. The energy consumption of high-pressure homogenization during pressure agglomeration is also high, resulting in significant equipment costs.

[0005] Polymer agglomeration is an excellent technique for preparing large-particle-size polybutadiene latex, and the polymer agglomerant used is a rubber latex particle containing a large number of free chain segments.

[0006] The method for preparing a single-peaked polybutadiene latex disclosed in patent CN104327281B uses an acrylic latex as the agglomerating agent in the agglomeration process, but does not involve the preparation method of the polymer agglomerating agent or the agglomeration process.

[0007] Patent US2002198309 discloses a method for increasing the particle size of butadiene latex by using butadiene-ethyl acrylate-methacrylic acid copolymer latex as a polymer agglomerant, but it directly uses seed-synthesized rubber latex for processing and does not provide a detailed preparation process for the polymer agglomerant.

[0008] Patent CN102050889B discloses a method for preparing ultra-large particle size polybutadiene latex, in which unsaturated organic acid ester-unsaturated organic acid-aryl ethylene latex is used as a polymer agglomerating agent to prepare ultra-large particle size latex with a particle size range of 400-1000nm.

[0009] Patent CN115651109B discloses a polymeric agglomerant that copolymerizes ethylene monomer with acrylic acid and acrylic acid derivatives, which can be used to prepare stable agglomerated latex, but it only improves the storage stability of agglomerated latex.

[0010] Currently, polymer agglomerates are mainly synthesized from acrylate monomers and acrylic acid derivatives. The large-particle-size latex prepared by these polymer agglomerates, and the ABS resin prepared by further processing it, has poor impact resistance at -5℃ and is not suitable for low-temperature environments, which limits its application in outdoor fields, automotive fields and electronic equipment fields.

[0011] Improving the impact and tensile properties of ABS resin, especially its low-temperature impact resistance, while enhancing the stability of the latex during and after polymerization using polymer agglomeration methods remains a problem to be solved. Summary of the Invention

[0012] The purpose of this invention is to provide a polymer agglomerant. Using 1,3-butadiene and α,β-unsaturated acid latex as polymer agglomerants, the stability of polybutadiene latex or polyacrylate latex during the agglomeration process can be further improved, and the slag rate reduced. Simultaneously, these latexes serve as the base latex for grafting different particle sizes, enabling the preparation of ABS and ASA resins with high impact strength and tensile strength, especially excellent low-temperature impact resistance.

[0013] The technical solution adopted in this invention is as follows:

[0014] In a first aspect, the present invention provides a polymer agglomerating agent emulsion:

[0015] A polymeric agglomerating agent emulsion, wherein 1,3-butadiene is the main polymerizing monomer, α,β-unsaturated acid is the comonomer, and the additives include emulsifier, initiator, and deionized water, with a final solid content of 30%-50% and a final pH value of 3-5.

[0016] As a preferred embodiment of the above technical solution, the monomer composition of the main polymerizing monomer and the comonomer is: 1,3-butadiene: 50-95 parts, comonomer: 10-50 parts;

[0017] More preferably, the monomer composition of the main polymerizing monomer and the comonomer is: 1,3-butadiene: 75-95 parts, comonomer: 20-30 parts.

[0018] As a preferred embodiment of the above technical solution, the comonomer includes one or a mixture of several of the following: acrylic acid, methacrylic acid, 3-phenyl-2-acrylic acid, 2-propenylacrylic acid, and crotonic acid. More preferably, the comonomer uses one or a mixture of acrylic acid and methacrylic acid.

[0019] As a preferred embodiment of the above technical solution, the polymer agglomerating agent emulsion comprises the following raw material components in parts by weight:

[0020] 100-500 parts deionized water, 50-95 parts 1,3-butadiene, 10-50 parts comonomer, 1-8 parts emulsifier, and 0.3-8 parts initiator;

[0021] More preferably, it includes: 100-300 parts of deionized water, 75-95 parts of 1,3-butadiene, 20-30 parts of comonomer, 3-6 parts of emulsifier, and 0.5-5 parts of initiator;

[0022] More preferably, it comprises: 150-300 parts of deionized water, 75-95 parts of 1,3-butadiene, 20-30 parts of comonomer, 3-6 parts of emulsifier, and 0.5-3 parts of initiator.

[0023] As a preferred embodiment of the above technical solution, the emulsifier is one or a mixture of any of the following: sodium dodecyl diphenyl ether disulfonate, sodium dodecylbenzene sulfonate, sodium dodecyl sulfate, sodium dihexyl succinate sulfonate, sodium alkylphenol ether sulfosuccinate, and DOSS. More preferably, the emulsifier used is one or a mixture of any two of the following: sodium dodecyl diphenyl ether disulfonate, sodium dodecylbenzene sulfonate, sodium dodecyl sulfate, and sodium dihexyl succinate sulfonate.

[0024] As a preferred embodiment of the above technical solution, the initiator includes:

[0025] Initiator A: 0.2-3.0 parts of cumene hydroperoxide; and Initiator B: 0.01-1 parts of ferrous sulfate heptahydrate, 0.1-3.0 parts of sodium formaldehyde sulfoxylate, and 0.001-1 parts of disodium ethylenediaminetetraacetate;

[0026] More preferably, it includes: initiator A: 0.3 to 1.5 parts of cumene hydroperoxide; and initiator B: 0.01 to 0.5 parts of ferrous sulfate heptahydrate, 0.1 to 1.5 parts of sodium formaldehyde sulfoxylate, and 0.05 to 0.5 parts of disodium ethylenediaminetetraacetate.

[0027] The preparation method of the polymer agglomerating agent emulsion specifically includes the following steps:

[0028] 1) Weigh the raw materials according to the weight ratio and set aside;

[0029] 2) Add the emulsifier, deionized water and initiator B to the high-pressure reactor, start stirring at 50-300 rpm to dissolve the emulsifier quickly, introduce nitrogen to remove the air in the reactor and heat the reactor to 50-70°C;

[0030] 3) Slowly add the polymer monomer 1,3-butadiene to the reactor, and simultaneously add the comonomer and initiator A dropwise over a period of 0.5 to 6 hours. After the addition is complete, raise the temperature to 60 to 80°C and keep it at that temperature for 1 to 2 hours. Cool to obtain a polymer agglomerator emulsion.

[0031] Secondly, the present invention provides the application of the above-mentioned polymer agglomerating agent emulsion.

[0032] The polymer agglomerating agent emulsion is mainly used for the preparation of large-particle-size latex, and the specific operation includes the following steps:

[0033] 1) Take 100 parts (dry basis weight) of polybutadiene latex or polyacrylate latex and place them in an agglomeration reactor;

[0034] 2) Add 0.1 to 10 parts (dry basis weight), preferably 2 to 5 parts, of the prepared polymer agglomerating agent emulsion to the agglomeration reactor, and agglomerate at 20 to 80°C for 30 to 120 minutes to obtain large particle size polybutadiene latex or polyacrylate latex.

[0035] The large-particle-size latex is mainly used for resin preparation, and the specific operation includes the following steps:

[0036] Large-particle-size polybutadiene latex or polyacrylate latex obtained by polymer agglomeration is grafted with copolymer monomers to obtain grafted latex; the grafted latex is coagulated and dried so that the moisture content of the final rubber powder is less than 1%; then the rubber powder, commercial grade SAN or MSAN resin and additive package are mixed, melt-blended, extruded and pelletized underwater, and dried again to obtain ABS or ASA resin.

[0037] The above operations are standard procedures in this field.

[0038] The beneficial effects of this invention are:

[0039] The polymer agglomerant emulsion prepared by this invention has good stability, and the latex particle size and mechanical stability do not change much within one month.

[0040] The agglomeration process can reduce latex residue and improve latex stability. By adjusting the amount of polymer agglomerant, the particle size of the latex can be controlled, which can effectively regulate the impact strength of the product, especially the low-temperature impact resistance, and prepare ABS and ASA resins with excellent physical properties and wider applications. Detailed Implementation

[0041] The technical solutions in the embodiments of the present invention will be clearly and completely described below. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention.

[0042] Analytical instruments:

[0043] Izod impact strength: CEAST 9050 pendulum impact tester;

[0044] Tensile strength: Instron 5966 universal testing machine;

[0045] Test method:

[0046] Izod impact strength: Standard ASTM D256;

[0047] Tensile strength: Standard ASTM D638;

[0048] Grafting rate test:

[0049] (1) Weigh the dried ABS powder (water content less than 1%, accurate to 0.0001 g, mass is G) and put it into a 100 ml flask. Add 50 mL of acetone along the neck of the flask, attach the condenser to the flask, and reflux in a 65 °C constant temperature water bath for 2.0 hours. During this period, do not allow the water bath temperature to exceed 65 °C, otherwise bumping may occur.

[0050] (2) Remove the flask and cool it to room temperature. Transfer the solution in the flask to a pre-weighed beaker and let it settle for 4 hours. Remove the supernatant. Place the beaker in a vacuum oven and dry it under vacuum at 65°C until constant weight. Weigh and calculate the dry basis mass as G1.

[0051] The grafted rubber content X (%) is calculated using the following formula:

[0052] Grafted rubber content X = G1 / G * 100%

[0053] In the formula: G1—grafted rubber mass (i.e., total of polybutyl acrylate and grafted SAN), unit: grams;

[0054] G—Sample mass (i.e., ABS grafting powder mass), unit: grams

[0055] Grafting rate π = [(Grafted rubber content - Formulated rubber content) / (Formulated rubber content)] × 100%

[0056] Solid content test:

[0057] The solid content was obtained by drying at 180°C using a Mettler HC103 moisture analyzer.

[0058] Slag content test:

[0059] After the agglomeration reaction is completed, the latex is filtered through a 100-mesh filter, and the filtered latex residue is dried in an oven at 80°C for 4 hours.

[0060] Slag content = m / M * 100%

[0061] m: Quality of adhesive residue on filter screen

[0062] M: Total mass of latex.

[0063] Example 1

[0064] The preparation method of polymer agglomerator A includes the following steps:

[0065] (1) Add 16g sodium dodecylbenzenesulfonate, 32g DOSS, initiator B (0.24g ferrous sulfate heptahydrate, 2.4g sodium formaldehyde sulfoxylate and 0.72g disodium ethylenediaminetetraacetate) to a high-pressure reactor, add 1600g deionized water, start the reactor and stir at 200rpm to dissolve it quickly, purge nitrogen to remove air from the reactor and heat the reactor to 60℃;

[0066] (2) Add 760g of 1,3-butadiene, a polymerizing monomer, to the reactor, and simultaneously add 160g of methacrylic acid, a copolymerizing functional monomer, and 4g of cumene hydroperoxide, an initiator. The addition time is 2 hours. After the addition is completed, maintain the reactor temperature at 60°C for 2 hours. After cooling, a polymer agglomerant with a pH of about 3.5 can be obtained.

[0067] The preparation method of polymer agglomerator B includes the following steps:

[0068] (1) Add 52g sodium dodecyl diphenyl ether disulfonate, initiator B (0.5g ferrous sulfate heptahydrate, 4.8g sodium formaldehyde sulfoxylate and 1g disodium ethylenediaminetetraacetate) to a high-pressure reactor, add 2000g deionized water, start the reactor and stir to 200rpm to dissolve it quickly, introduce nitrogen to remove air from the reactor and heat the reactor to 60℃;

[0069] (2) Add 800g of 1,3-butadiene, a monomer, to the reactor, and simultaneously add 200g of methacrylic acid, a copolymer functional monomer, and 5.7g of cumene hydroperoxide, an initiator. The addition time is 2 hours. After the addition is completed, maintain the reactor temperature at 60°C for 2 hours. After cooling, a polymer agglomerant with a pH of about 4.2 can be obtained.

[0070] The preparation method of polymer agglomerator C includes the following steps:

[0071] (1) Add 30g sodium dodecyl sulfate, 10g DOSS, initiator B (1g ferrous sulfate heptahydrate, 12g sodium formaldehyde sulfoxylate and 4.8g disodium ethylenediaminetetraacetate) to a high-pressure reactor, add 1800g deionized water, start the reactor and stir to 200rpm to dissolve it quickly, introduce nitrogen to remove air from the reactor and heat the reactor to 60℃;

[0072] (2) Add 900g of 1,3-butadiene, a monomer, to the reactor, and simultaneously add 300g of methacrylic acid, a copolymer functional monomer, and 8g of cumene hydroperoxide, an initiator. The addition time is 2 hours. After the addition is completed, maintain the reactor temperature at 60°C for 2 hours. After cooling, a polymer agglomerant with a pH of about 3.6 can be obtained.

[0073] Example 2

[0074] The preparation of large-particle-size polybutadiene latex includes the following process:

[0075] (1) The polymerization method of polybutadiene latex to be agglomerated is as follows: 20g of emulsifier disproportionated rosin acid potassium soap, 20g of fatty acid potassium soap, 8g of electrolyte potassium carbonate, 2g of molecular weight regulator tert-dodecyl mercaptan, and 2.5g of initiator potassium persulfate are placed in a high-pressure reactor. After adding 1500g of deionized water, the temperature is rapidly raised to 65℃. Then, 1000g of butadiene monomer is added. After keeping the temperature for 12h, the material is discharged to obtain polybutadiene latex, which is the latex to be agglomerated. The average particle size of the latex to be agglomerated is 105nm.

[0076] (2) Take 100g of latex to be agglomerated (dry basis, adjust solid content to 55%) and place it in the agglomeration kettle. Add 3g of polymer agglomerating agent A (dry basis) prepared in Example 1 to the agglomeration kettle. After agglomerating at 50°C for 30min, large particle size polybutadiene latex can be obtained, and the residue content in the process can be calculated.

[0077] Examples 3 to 6

[0078] According to the formulation of agglomerating agent dosage and type in Table 1, large particle size polybutadiene latexes of Examples 3 to 6 were prepared respectively, with the remaining conditions being the same as those of Example 2.

[0079] Table 1. Amount of polymer agglomerating agent used in Examples 3 to 6

[0080] Example 3 Example 4 Example 5 Example 6 Dry weight of agglomerating agent (g) 3 (Agglomerating agent B) 3 (Agglomerating agent C) 4 (Agglomerating agent A) 5 (Agglomerating agent A)

[0081] Comparative Example 1

[0082] Acrylic esters and acrylic polymeric polymeric polymeric agents were prepared according to the method in Example 1 of the patent "Preparation of acrylate polymeric agents and their use in the polymerization of polyacrylate latex" (CN102321211B).

[0083] Comparative Example 2

[0084] Ethylene and acrylic acid polymeric agglomerants were synthesized according to the method in Example 1 of the patent "Agglomerant for the production of elastomers and preparation method thereof" (CN 115651109 B).

[0085] Comparative Example 3

[0086] The preparation of large-particle-size polybutadiene latex includes the following process:

[0087] Take 100g of latex to be agglomerated (same as in Example 2, dry basis, with the solid content adjusted to 55%) and place it in an agglomeration reactor. Add 3g (dry basis) of the polymer agglomerating agent prepared in Comparative Example 1 to the agglomeration reactor. After agglomerating at 50°C for 30 minutes, large-particle-size polybutadiene latex can be obtained, and the residue content during the process can be calculated.

[0088] Comparative Example 4

[0089] The preparation of large-particle-size polybutadiene latex includes the following process:

[0090] Take 100g of latex to be agglomerated (same as in Example 2, dry basis, with the solid content adjusted to 55%) and place it in an agglomeration reactor. Add 3g (dry basis) of the polymer agglomerating agent prepared in Comparative Example 2 to the agglomeration reactor. After agglomerating at 50°C for 30 minutes, large-particle-size polybutadiene latex can be obtained, and the residue content during the process can be calculated.

[0091] Comparative Example 5

[0092] Take 100g of latex to be agglomerated (same as in Example 2, dry basis, with the solid content adjusted to 55%) and place it in an agglomeration reactor. Add 7g of 2% acetic acid to the agglomeration reactor and agglomerate at room temperature for 30 minutes. Then, add 11g of 7% KOH to terminate the agglomeration. Large-particle-size polybutadiene latex can be obtained, and the residue content during the process can be calculated.

[0093] Comparative Example 6

[0094] Take 100g of latex to be agglomerated (same as in Example 2, dry basis, with the solid content adjusted to 55%) and place it in an agglomeration reactor. Add 2g of DOSS as a stabilizer, add 7g of 2% acetic acid to the agglomeration reactor, agglomerate at room temperature for 30 minutes, and then add 11g of 7% KOH to terminate the agglomeration. Large-particle-size polybutadiene latex can be obtained, and the residue content during the process can be calculated.

[0095] Experimental Examples

[0096] Preparation of grafted ABS latex:

[0097] (1) Add 60 parts of large particle size polybutadiene latex (dry basis, with the solid content adjusted to 45%), 240 parts of water, 0.2 parts of potassium oleate, 0.02 parts of cumene hydroperoxide, 0.015 parts of glucose, 0.01 parts of sodium pyrophosphate and 0.005 parts of ferrous sulfate heptahydrate to the reaction vessel and heat to 50°C.

[0098] (2) Add dropwise a mixture of 40 parts styrene and 10 parts acrylonitrile. The addition should be completed within 2 hours. After the addition is completed, keep the temperature at 70°C for 0.5 hours. Stop the reaction after the monomer is consumed.

[0099] Coagulation and Drying: The prepared grafted emulsion was coagulated by adding 5% dilute sulfuric acid at 70℃, followed by vacuum filtration and fluidized bed drying (air velocity 180 m / s). 3 After drying at 70℃ for 0.5-1h, ABS grafted powder is obtained.

[0100] ABS resin was prepared by blending and granulation: 24 parts by weight of the above-mentioned ABS grafted powder, 76 parts by weight of 80HF (LG Chem), 0.1 parts by weight of antioxidant 1076 (BASF, Germany), 0.1 parts by weight of antioxidant 618 (Panhua Chemical (Shanghai) Co., Ltd.), 0.2 parts by weight of magnesium oxide, and 2 parts by weight of N,N-ethylene bis-stearamide (Shandong Li'ang New Material Co., Ltd.) were kneaded in a high-speed kneader for 5 minutes. The mixture was then melt-granulated and blended in a twin-screw extruder at 220°C to obtain ABS resin granules. The granules were dried in an oven at 80°C for 2 hours, and then injection-molded for mechanical property testing.

[0101] The particle size and residue content of the large-particle-size latexes prepared in Examples 2 to 6 and Comparative Examples 3 to 6 were tested respectively; the ABS resins prepared by the large-particle-size latexes prepared in Examples 2 to 6 and Comparative Examples 3 to 6 according to the above method were tested respectively, and the properties are shown in Table 2.

[0102] Table 2: Performance Test Results of Examples and Comparative Examples

[0103]

[0104]

[0105] As shown in Table 2, the polymer agglomerating agent prepared by copolymerizing butadiene and α,β-unsaturated acid according to the present invention can be used to prepare large-particle-size polybutadiene latex. It is stable during the agglomeration process, with low slag output, which can improve production efficiency and improve the mechanical properties (impact resistance and tensile strength) of ABS. In particular, it can improve the impact resistance of ABS under low-temperature conditions, further expanding the application range of ABS.

[0106] It is readily understood that the above embodiments are merely illustrative examples for clear explanation and do not imply that the invention is limited thereto. 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 polymer agglomerant emulsion, characterized in that, The raw materials for its preparation are 1,3-butadiene as the main polymer monomer and α,β-unsaturated acid as the comonomer. The auxiliary agents include emulsifier, initiator and deionized water; the pH value of the emulsion is 3-5.

2. The polymer agglomerant emulsion according to claim 1, characterized in that, The amount of polymerizable monomers is: 50-95 parts for 1,3-butadiene and 10-50 parts for comonomers.

3. The polymer agglomerant emulsion according to claim 1, characterized in that, The polymer agglomerating agent comprises the following raw materials in parts by weight: 100-500 parts deionized water, 50-95 parts 1,3-butadiene, 10-50 parts comonomer, 1-8 parts emulsifier, and 0.3-8 parts initiator.

4. The polymer agglomerating agent emulsion according to claim 3, characterized in that, The polymer agglomerating agent comprises the following raw materials in parts by weight: 100-300 parts deionized water, 75-95 parts 1,3-butadiene, 20-30 parts comonomer, 3-6 parts emulsifier, and 0.5-5 parts initiator.

5. The polymer agglomerant emulsion according to claim 4, characterized in that, The polymer agglomerating agent comprises the following raw materials in parts by weight: 150-300 parts deionized water, 75-95 parts 1,3-butadiene, 20-30 parts comonomer, 3-6 parts emulsifier, and 0.5-3 parts initiator.

6. The polymer agglomerant emulsion according to any one of claims 1-5, characterized in that, The comonomer includes at least one of acrylic acid, methacrylic acid, 3-phenyl-2-acrylic acid, 2-propenylacrylic acid, and crotonic acid.

7. The polymer agglomerant emulsion according to any one of claims 1-5, characterized in that, The emulsifier is at least one of sodium dodecyl diphenyl ether disulfonate, sodium dodecyl benzene sulfonate, sodium dodecyl sulfate, sodium dihexyl succinate sulfonate, sodium alkylphenol ether sulfosuccinate, and DOSS.

8. The polymer agglomerant emulsion according to any one of claims 1-5, characterized in that, The initiator includes: Initiator A: 0.2–3.0 parts of cumene hydroperoxide; Initiator B: 0.01-1 part ferrous sulfate heptahydrate, 0.1-3.0 part sodium formaldehyde sulfoxylate, and 0.001-1 part disodium ethylenediaminetetraacetate.

9. The polymer agglomerant emulsion according to claim 8, characterized in that, The initiator includes: Initiator A: 0.3–1.5 parts of cumene hydroperoxide; Initiator B: 0.01-0.5 parts ferrous sulfate heptahydrate, 0.1-1.5 parts sodium formaldehyde sulfoxylate, and 0.05-0.5 parts disodium ethylenediaminetetraacetate.

10. The method for preparing the polymer agglomerant emulsion according to any one of claims 1 to 9, characterized in that, Includes the following steps: 1) Weigh the raw materials according to the specified weight ratio and set aside; 2) Add the emulsifier, deionized water and initiator B to the high-pressure reactor, start stirring at 50-300 rpm to dissolve the emulsifier quickly, introduce nitrogen to remove the air in the reactor and heat the reactor to 50-70°C; 3) Slowly add the polymer monomer 1,3-butadiene to the reactor, and simultaneously add the comonomer and initiator A dropwise. After the addition is complete, raise the temperature to 60-80℃ and keep it at that temperature for 1-2 hours; cool to obtain a polymer agglomerator emulsion.

11. A method for preparing large-particle-size latex, characterized in that, Includes the following steps: 1) Take 100 parts of polybutadiene latex or polyacrylate latex and place them in an agglomeration reactor, wherein the amount refers to the dry basis weight; 2) Add 0.1 to 10 parts of the polymer agglomerating agent emulsion according to any one of claims 1-9 to the agglomeration reactor, and agglomerate at 20 to 80°C for 30 to 120 minutes to obtain large particle size polybutadiene latex or polyacrylate latex, wherein the amount refers to the dry basis weight.

12. The preparation method according to claim 11, wherein, Step 2) The amount of polymer agglomerant used is 2-5 parts, and the amount refers to the dry basis weight.

13. A method for preparing ABS or ASA resin, characterized in that, It is prepared using the large-particle-size polybutadiene latex or polyacrylate latex prepared according to claim 11.

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