High-molecular agglomerant as well as preparation method and application thereof

Abstract

The invention provides a macromolecular agglomerant and a preparation method thereof. The high-molecular agglomerant takes 1, 3-butadiene as a main polymeric monomer and alpha, beta-unsaturated acid as a comonomer, and assistants comprise an emulsifier, an initiator and deionized water. The macromolecular agglomerant is used for further preparing large-particle-size polybutadiene latex and polyacrylate latex, the components are simple, introduction of more new monomers is reduced, the stability of the latex in the agglomeration process is improved, then ABS and ASA resin is prepared, the impact resistance and tensile property of the ABS and ASA resin are improved, and particularly the impact resistance under the low-temperature working condition is improved.

Description

Technical Field

[0001] The invention belongs to the technical field of engineering plastics ABS, and particularly relates to the preparation and application of an agglomerating agent in the preparation process of large-particle ABS. Background Art

[0002] ABS resin is a copolymer of acrylonitrile-butadiene-styrene. It is a thermoplastic polymer material with high strength, good toughness, and easy processing and molding. It has good moldability and is mainly used for alloys and plastics. The synthesis methods of ABS resin are mainly divided into two types: continuous bulk method and emulsion blending method. Among them, the technical process of preparing ABS resin by emulsion blending method is the most widely used. The key to preparing ABS resin by emulsion blending method lies in the preparation of ABS rubber powder in the process of preparing ABS resin. Generally speaking, ABS rubber powder is mainly obtained by emulsion grafting of large-particle polybutadiene latex.

[0003] The preparation methods of large-particle polybutadiene latex are divided into one-step method and two-step method. Among them, the one-step method of preparing large-particle polybutadiene latex originated from the Japanese JSR technology process, which is to polymerize butadiene monomer under high emulsifier concentration through emulsion polymerization technology, and add monomers or emulsifiers in the process to make the final polybutadiene latex particle size reach 300nm, and the solid content is as high as 50-60%. Its advantages are that the prepared latex has a narrow particle size distribution and good stability, and its disadvantages are that the preparation cycle is long and the efficiency is low.

[0004] The two-step method for preparing large-particle polybutadiene latex is to first prepare small-particle polybutadiene latex (particle size is between 70-150nm), preferably 90-110nm, and then use an agglomerating agent such as acetic acid, electrolyte or high-pressure homogenization to agglomerate the small-particle polybutadiene latex into large-particle polybutadiene latex. The advantage of this process is that the polymerization rate is fast. The time for the entire polymerization process is 14-16 hours, which is half of the one-step method for preparing large-particle latex. However, its disadvantages are also more prominent. For example, the wastewater produced by the latex after acetic acid or electrolyte agglomeration contains a large amount of salt, which increases the cost of wastewater treatment. The energy consumption of using high-pressure homogenization during pressure agglomeration is high, and the equipment cost is prominent.

[0005] The polymer agglomeration method is an excellent technology for preparing large-particle polybutadiene latex. The polymer agglomerating agent used is rubber latex particles containing a large number of free chain segments.

[0006] Patent CN104327281B discloses a method for preparing a polybutadiene latex with a unimodal distribution. The agglomerating agent used in the agglomeration process is an acrylic latex, but does not involve a preparation method and an agglomeration process of a polymer agglomerating agent.

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

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

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

[0010] At present, polymer agglomerates are mainly synthesized from acrylate monomers and acrylic acid derivatives. The large-particle latex prepared by such polymer agglomerates and the ABS resin further prepared have poor impact resistance at -5°C and are not suitable for low-temperature environments, which imposes certain restrictions on their application in outdoor fields, automotive fields, electronic equipment and other fields.

[0011] Using polymer agglomeration method to improve the stability of latex during and after agglomeration while improving the impact resistance and tensile properties of ABS resin, especially low-temperature impact resistance, is still a problem that needs to be solved. Summary of the invention

[0012] The purpose of the present invention is to provide a polymer agglomerating agent. The polymer agglomerating method can be used to further improve the stability of polybutadiene latex or polyacrylate latex in the agglomeration process, reduce the slag rate, and at the same time, use it as a base latex for grafting large and small particle sizes to prepare ABS and ASA resins with high impact strength and tensile strength, especially excellent low-temperature impact resistance.

[0013] The technical solution adopted by the present invention is as follows:

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

[0015] A polymer agglomerating agent emulsion, wherein 1,3-butadiene is a main polymerization monomer, α,β-unsaturated acid is a copolymerization monomer, auxiliary agents include emulsifier, initiator, deionized water, the final solid content is 30%-50%, and the final pH value is 3-5.

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

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

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

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

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

[0021] More preferably, it comprises: 100 to 300 parts of deionized water, 75 to 95 parts of 1,3-butadiene, 20 to 30 parts of comonomer, 3 to 6 parts of emulsifier, and 0.5 to 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 technical solution of the above technical solution, the emulsifier is one of sodium dodecyl diphenyl oxide disulfonate, sodium dodecyl benzene sulfonate, sodium dodecyl sulfate, sodium dihexyl sulfosuccinate, sodium salt of alkylphenol ether sulfosuccinate, DOSS, or any mixture of any two thereof. More preferably, the emulsifier used is one of sodium dodecyl diphenyl oxide disulfonate, sodium dodecyl benzene sulfonate, sodium dodecyl sulfate, sodium dihexyl sulfosuccinate, or any mixture of any two thereof.

[0024] As a preferred technical solution 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, 0.001-1 parts of disodium ethylenediaminetetraacetate;

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

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

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

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

[0030] 3) Slowly add the polymerization monomer 1,3-butadiene to the reactor, and simultaneously drop the comonomer and initiator A for 0.5 to 6 hours. After the dropwise addition is completed, heat to 60 to 80° C. and keep warm for 1 to 2 hours; cool to obtain a polymer agglomerating agent emulsion.

[0031] In a second aspect, the present invention provides the use 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) 100 parts (dry basis weight) of polybutadiene latex or polyacrylate latex are placed in an agglomeration kettle;

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

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

[0036] The grafted latex is obtained by grafting copolymerized monomers with large-particle polybutadiene latex or polyacrylate latex after polymer agglomeration; the grafted latex is condensed and dried to make the moisture content of the final rubber powder lower than 1%; then the rubber powder, commercial-grade SAN or MSAN resin and an additive package are mixed and melt-blended, extruded and pelletized underwater, and dried again to obtain ABS or ASA resin.

[0037] The above operations are routine operations in this field.

[0038] Beneficial effects of the present invention:

[0039] The polymer agglomerating agent emulsion prepared by the present invention has good stability, and the particle size of the latex, mechanical stability and the like do not change much after being placed for one month.

[0040] The latex slag can be reduced during the agglomeration process, and the latex stability during the agglomeration process is improved. The particle size of the latex can be regulated by adjusting the dosage of the polymer agglomerating agent, and the impact strength of the product, especially the low-temperature impact resistance, can be effectively adjusted to prepare ABS and ASA resins with excellent physical properties and wider applications. DETAILED DESCRIPTION

[0041] The technical solutions in the embodiments of the present invention are described clearly and completely below. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work 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 material 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 place it in a 100 ml flask. Add 50 ml of acetone along the neck of the flask. Install a condenser on the flask and reflux in a 65 °C constant temperature water bath for 2.0 hours. During this period, do not let the water bath temperature exceed 65 °C, otherwise violent boiling may occur.

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

[0051] The grafted rubber content X (%) is calculated as follows:

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

[0053] Where: G1—grafted rubber mass (i.e. total of polybutyl acrylate and grafted SAN), unit: g;

[0054] G—sample mass (i.e. ABS grafted powder mass), unit: gram

[0055] Grafting rate π = [(grafted rubber content - formula 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 was completed, the latex was filtered through a 100-mesh filter, and the filtered rubber residue was dried in an oven at 80°C for 4 h;

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

[0061] m: The mass of the rubber residue on the filter

[0062] M: total mass of latex.

[0063] Example 1

[0064] The preparation method of polymer agglomerating agent A comprises:

[0065] (1) 16 g of sodium dodecylbenzene sulfonate, 32 g of DOSS, and initiator B (0.24 g of ferrous sulfate heptahydrate, 2.4 g of sodium formaldehyde sulfoxylate, and 0.72 g of disodium ethylenediaminetetraacetate) were added to an autoclave, and 1600 g of deionized water was added. The autoclave was stirred at 200 rpm to dissolve the mixture rapidly, and nitrogen was introduced to remove air from the autoclave, and the autoclave was heated to 60° C.;

[0066] (2) Add 760 g of polymerizable monomer 1,3-butadiene to the reactor, simultaneously add 160 g of copolymerizable functional monomer methacrylic acid and 4 g of initiator A cumene hydroperoxide, and the addition time is 2 hours. After the addition is completed, the reactor temperature is maintained at 60° C. for 2 hours. After cooling, a high molecular weight agglomerating agent is obtained, and the pH value is about 3.5.

[0067] The preparation method of polymer agglomerating agent B comprises:

[0068] (1) 52 g of sodium dodecyl diphenyl oxide disulfonate, initiator B (0.5 g of ferrous sulfate heptahydrate, 4.8 g of sodium formaldehyde sulfoxylate and 1 g of disodium ethylenediaminetetraacetate) were added to a high-pressure reactor, and 2000 g of deionized water was added. The reactor was stirred at 200 rpm to dissolve rapidly, and nitrogen was introduced to remove air from the reactor and the reactor was heated to 60° C.;

[0069] (2) Add 800 g of polymerizable monomer 1,3-butadiene to the reactor, simultaneously add 200 g of copolymerizable functional monomer methacrylic acid and 5.7 g of initiator A cumene hydroperoxide, and the addition time is 2 hours. After the addition is completed, the reactor temperature is maintained at 60° C. for 2 hours. After cooling, a polymer agglomerating agent is obtained, and the pH value is about 4.2.

[0070] The preparation method of polymer agglomerating agent C comprises:

[0071] (1) 30 g of sodium dodecyl sulfate, 10 g of DOSS, initiator B (1 g of ferrous sulfate heptahydrate, 12 g of sodium formaldehyde sulfoxylate, and 4.8 g of disodium ethylenediaminetetraacetate) were added to a high-pressure reactor, and 1800 g of deionized water was added. The reactor was stirred at 200 rpm to dissolve rapidly, and nitrogen was introduced to remove air from the reactor and the reactor was heated to 60° C.;

[0072] (2) Add 900 g of polymerizable monomer 1,3-butadiene, 300 g of copolymerizable functional monomer methacrylic acid, and 8 g of initiator A cumene hydroperoxide to the reactor dropwise for 2 hours. After the addition is completed, maintain the reactor temperature at 60° C. for 2 hours. After cooling, a polymer agglomerating agent is obtained, and the pH value is about 3.6.

[0073] Example 2

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

[0075] (1) The polymerization method of the polybutadiene latex to be agglomerated is as follows: 20 g of an emulsifier, potassium soap of disproportionate rosin acid, 20 g of a fatty acid potassium soap, 8 g of an electrolyte potassium carbonate, 2 g of a molecular weight regulator, and 2.5 g of an initiator potassium persulfate are placed in a high-pressure reactor, 1500 g of deionized water is added, and the temperature is rapidly raised to 65° C., 1000 g of a butadiene monomer is added, and the mixture is discharged after being kept warm for 12 hours to obtain a polybutadiene latex, i.e., the latex to be agglomerated. The average particle size of the latex to be agglomerated is 105 nm.

[0076] (2) 100 g of the latex to be agglomerated (dry basis, adjusted to a solid content of 55%) is placed in an agglomeration kettle, and 3 g (dry basis) of the polymer agglomerator A prepared in Example 1 is added to the agglomeration kettle. After agglomeration at 50° C. for 30 min, a large-particle polybutadiene latex is obtained, and the slag content during the process is calculated.

[0077] Example 3 to Example 6

[0078] According to the dosage and type of agglomerating agent in Table 1, large particle size polybutadiene latex of Examples 3 to 6 were prepared respectively, and the other conditions were 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 Agglomerant dry basis mass (g) 3(Agglomerating agent B) 3(Agglomerating agent C) 4(Agglomerating agent A) 5(Agglomerating agent A)

[0081] Comparative Example 1

[0082] Acrylic acid ester and acrylic polymer agglomerating agent were prepared according to the method of Example 1 of the patent "Preparation of acrylic acid ester agglomerating agent and its application in agglomeration of polyacrylate latex" (CN102321211B).

[0083] Comparative Example 2

[0084] Ethylene and acrylic acid polymer agglomerating agents were synthesized according to the method of Example 1 of the patent "Agglomerating agent for producing elastomers and preparation method thereof" (CN 115651109 B).

[0085] Comparative Example 3

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

[0087] Take 100g of the latex to be agglomerated (same as Example 2. Dry basis, adjust the solid content to 55%) and place it in an agglomeration kettle. Add 3g (dry basis) of the polymer agglomerator prepared in Comparative Example 1 into the agglomeration kettle. After agglomeration at 50°C for 30 minutes, large-particle polybutadiene latex can be obtained, and the slag content in the process is calculated.

[0088] Comparative Example 4

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

[0090] Take 100g of the latex to be agglomerated (same as Example 2. Dry basis, adjust the solid content to 55%) and place it in an agglomeration kettle. Add 3g (dry basis) of the polymer agglomerator prepared in Comparative Example 2 into the agglomeration kettle. After agglomeration at 50°C for 30 minutes, large-particle polybutadiene latex can be obtained, and the slag content in the process is calculated.

[0091] Comparative Example 5

[0092] Take 100g of the latex to be agglomerated (same as Example 2. Dry basis, adjust the solid content to 55%) and place it in an agglomeration kettle. Add 7g of 2% acetic acid into the agglomeration kettle. After agglomeration at room temperature for 30 minutes, add 11g of 7% KOH to terminate the agglomeration. A large-particle polybutadiene latex can be obtained, and the slag content in the process is calculated.

[0093] Comparative Example 6

[0094] Take 100g of the latex to be agglomerated (same as Example 2. Dry basis, adjust the solid content to 55%) and place it in an agglomeration kettle, add 2g of DOSS as a stabilizer, add 7g of 2% acetic acid to the agglomeration kettle, agglomerate at room temperature for 30 minutes, then add 11g of 7% KOH to terminate the agglomeration, and a large-particle polybutadiene latex can be obtained, and the slag content in the process is calculated.

[0095] Experimental Examples

[0096] Preparation of grafted ABS latex:

[0097] (1) 60 parts of large particle size polybutadiene latex (dry basis, adjusted to a solid content of 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 were added to a reaction kettle and the temperature was raised to 50° C.;

[0098] (2) A mixture of 40 parts of styrene and 10 parts of acrylonitrile was added dropwise within 2 hours. After the addition was completed, the temperature was kept at 70° C. for 0.5 hours. The reaction was stopped after the monomers were consumed.

[0099] Coagulation and drying: The prepared grafted emulsion was coagulated by adding 5% dilute sulfuric acid at 70°C, vacuum filtered, and fluidized bed dried (wind speed 180m 3 / h, temperature 70°C, drying time 0.5-1h) to obtain ABS grafted powder.

[0100] Preparation of ABS resin by blending and granulation: 24 parts by mass of the above ABS grafted powder, 76 parts by mass of 80HF (LG Chemical), 0.1 parts of antioxidant 1076 (BASF, Germany), 0.1 parts of antioxidant 618 (Panhua Chemical (Shanghai) Co., Ltd.), 0.2 parts of magnesium oxide, and 2 parts of N,N-ethylene bisstearic acid amide (Shandong Liang New Materials Co., Ltd.) were kneaded in a high-speed kneader for 5 minutes, and then the mixture was melt-granulated and blended at 220°C in a twin-screw extruder, granulated, and finally ABS resin pellets were obtained. The above pellets were dried in an oven at 80°C for 2 hours, and mechanical properties were tested after injection molding.

[0101] The particle size and slag content of the large-particle latex prepared in Examples 2 to 6 and Comparative Examples 3 to 6 were tested respectively; the ABS resin prepared according to the above method using the large-particle latex prepared in Examples 2 to 6 and Comparative Examples 3 to 6 was 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 can be seen from Table 2, the polymer agglomerating agent prepared by copolymerization of butadiene and α, β-unsaturated acid of the present invention can be used to prepare large-particle polybutadiene latex, which is stable during the agglomeration process and has a low slag amount, thereby improving production efficiency and the mechanical properties (impact resistance and tensile strength) of ABS, especially improving the impact resistance of ABS under low temperature conditions, thereby further broadening the application scope of ABS.

[0106] It is easy to understand that the above embodiments are only examples for clear explanation and do not mean that the present invention is limited thereto. For ordinary technicians in the relevant field, other different forms of changes or modifications can be made based on the above description. It is not necessary and impossible to list all the implementation methods here. The obvious changes or modifications derived from this are still within the protection scope of the present invention.

Claims

1. A polymer agglomerating agent emulsion, characterized in that: The preparation raw materials use 1,3-butadiene as the main polymerization monomer, α, β-unsaturated acid as the copolymerization monomer, and the auxiliary agents include emulsifier, initiator, and deionized water; the pH value of the emulsion is 3-5.

2. The polymer agglomerating agent emulsion according to claim 1, characterized in that The main monomer dosage is: 1,3-butadiene: 50-95 parts, comonomer: 10-50 parts.

3. The polymer agglomerating agent emulsion according to claim 1 or 2, characterized in that: The polymer agglomerating agent comprises the following raw materials in parts by weight: 100 to 500 parts of deionized water, 50 to 95 parts of 1,3-butadiene, 10 to 50 parts of comonomer, 1 to 8 parts of emulsifier, and 0.3 to 8 parts of initiator; Preferably, it comprises: 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; 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.

4. The polymer agglomerating agent emulsion according to any one of claims 1 to 3, characterized in that: The comonomer includes at least one of acrylic acid, methacrylic acid, 3-phenyl-2-acrylic acid, 2-propenyl acrylic acid, and crotonic acid, preferably acrylic acid and / or methacrylic acid.

5. The polymer agglomerating agent emulsion according to any one of claims 1 to 3, characterized in that: The emulsifier is at least one of sodium dodecyl diphenyl ether disulfonate, sodium dodecylbenzene sulfonate, sodium dodecyl sulfate, sodium dihexyl sulfosuccinate, sodium salt of alkylphenol ether sulfosuccinate, and DOSS.

6. The polymer agglomerating agent emulsion according to any one of claims 1 to 3, characterized in that: The initiator comprises: Initiator A: 0.2-3.0 parts of cumene hydroperoxide; and initiator B: 0.01-1 part of ferrous sulfate heptahydrate, 0.1-3.0 parts of sodium formaldehyde sulfoxylate, 0.001-1 part of disodium ethylenediaminetetraacetate; More preferably, it includes: Initiator A: 0.3-1.5 parts of cumene hydroperoxide; And initiator B: 0.01-0.5 parts of ferrous sulfate heptahydrate, 0.1-1.5 parts of sodium formaldehyde sulfoxylate, and 0.05-0.5 parts of disodium ethylenediaminetetraacetate.

7. The method for preparing a polymer agglomerating agent emulsion according to any one of claims 1 to 6, characterized in that: The following steps are involved: 1) weigh the raw materials according to the weight ratio and set aside; 2) Add emulsifier, deionized water and initiator B into the autoclave, start stirring at 50-300 rpm to dissolve the emulsifier quickly, introduce nitrogen to remove air in the autoclave and heat the autoclave to 50-70° C.; 3) Slowly add the polymerization monomer 1,3-butadiene to the reactor, and simultaneously drop the comonomer and initiator A. After the dropwise addition is completed, heat to 60-80° C. and keep warm for 1-2 hours; cool to obtain a polymer agglomerating agent.

8. A method for preparing a large particle size latex, characterized in that: The steps include: 1) 100 parts (dry basis) of polybutadiene latex or polyacrylate latex are placed in an agglomeration kettle; 2) Add 0.1 to 10 parts (dry basis), preferably 2 to 5 parts, of the polymer agglomerating agent described in any one of claims 1 to 6 into an agglomeration kettle, and agglomerate at 20 to 80° C. for 30 to 120 minutes to obtain a large-particle polybutadiene latex or polyacrylate latex.

9. A method for preparing ABS or ASA resin, characterized in that: The method is prepared by using the large-particle polybutadiene latex or polyacrylate latex prepared according to claim 8.

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