Soap-free macromolecular agglomerant as well as preparation method and application thereof

Abstract

The invention provides a soap-free high-molecular agglomerant as well as a preparation method and application thereof. The soap-free high-molecular agglomerant contains an oligomer, the molecular structure of the oligomer contains a hydrophilic group and an oleophylic group; the weight-average molecular weight of the oligomer is 300 to 5000; the hydrophilic group comprises an amide group and / or carboxyl. According to the invention, the soap-free high-molecular agglomerant has a good agglomeration effect, large-particle-size polybutadiene latex can be obtained through agglomeration, and the high-molecular agglomerant does not contain an emulsifier, so that the introduction of excessive emulsifier in the preparation process of an ABS graft polymer is avoided; the ABS latex coagulation efficiency is improved, the impact resistance of the ABS resin is improved, and the yellow index of the ABS resin is reduced.

Description

Technical Field

[0001] The present invention belongs to the technical field of polymer materials, and particularly relates to a soap-free polymer agglomerating agent, a preparation method thereof, and an application thereof. Background Art

[0002] ABS resin is one of the five major synthetic resins in the world, and is a graft copolymer of polybutadiene latex (PBL latex) with styrene and acrylonitrile. ABS resin is a polymer material between general plastics and engineering plastics, and has excellent impact resistance, heat resistance, chemical resistance and other properties. Moreover, as the particle size of the rubber core increases, the impact resistance of ABS resin increases accordingly. Therefore, when preparing ABS resin from PBL latex as a raw material, a one-step method or a two-step method is adopted to pre-prepare PBL latex with a large particle size in advance, so as to improve the performance of ABS resin.

[0003] For the one-step method for preparing PBL latex with a large particle size, before the 1980s, it took more than 40 hours to reach 300 nm. With the progress of technology, although the reaction time can be shortened to about 20 hours at present, it is still a constraint on production capacity improvement for production. For the two-step method for preparing PBL latex with a large particle size, one step is to enlarge small particle size PBL by using the agglomeration method to obtain PBL latex with a large particle size. The existing agglomeration methods include physical agglomeration, such as pressure agglomeration, freezing agglomeration, mechanical stirring agglomeration, etc.; chemical agglomeration, such as acid agglomeration, organic solvent agglomeration, etc.; polymer agglomeration methods, such as non-ionic latex, unsaturated carboxylic acid copolymer latex, etc. Among them, polymer agglomeration is an agglomeration method with good application and the widest application.

[0004] For example, Patent CN113754797A provides a polymer agglomerating agent latex, which uses ethyl acrylate and methyl methacrylate as raw materials and obtains a polymer agglomerating agent through emulsion polymerization according to a certain ratio; the polymer agglomerating agent can expand the diameter of latex with a particle size of 80-110 nm to 280-330 m after agglomerating for half an hour. However, the polymer agglomerating agent latex contains an emulsifier, and the emulsifier is likely to cause secondary nucleation during subsequent graft polymerization, generating small particle size latex particles, which will not only affect the coagulation process; but also affect the performance of the final product, such as yellowness, mechanical properties, gloss, aesthetics, etc.

[0005] Patent CN113651903A provides a method for preparing large particle size polybutadiene latex based on polymer agglomeration technology, which uses vinyl sulfate or vinyl sulfonate as a reactive emulsifier and an ionic comonomer to replace the traditional acrylic comonomer, avoiding the use of any adsorptive emulsifier. Although the agglomerating agent obtained by the method can improve the influence of the emulsifier on the material properties to a certain extent, it still uses an emulsifier monomer, and the improvement effect needs to be further improved.

[0006] Therefore, it is an urgent problem to be solved in this field to develop a polymer coagulant that does not require the introduction of an emulsifier, does not affect the ABS latex coagulation process, and can improve the impact resistance of the ABS resin material and reduce the yellowness of the ABS resin. Summary of the Invention

[0007] Aiming at the deficiencies of the existing technology, the purpose of the present invention is to provide a soap-free polymer agglomerant and its preparation method and application. The soap-free polymer agglomerant has good agglomeration effect, can agglomerate to obtain polybutadiene latex with large particle size, and the obtained agglomerated polybutadiene latex has good stability; and the polymer agglomerant does not contain an emulsifier, avoiding the formation of SAN polymer and small particle size latex particles due to excessive introduction of emulsifier during the preparation of ABS graft polymer; it is beneficial to improve the coagulation efficiency of ABS latex and improve the properties of ABS resin.

[0008] To achieve this purpose, the present invention adopts the following technical solutions:

[0009] The present invention provides a soap-free polymer agglomerant, and the soap-free polymer agglomerant contains oligomers; the molecular structure of the oligomers contains hydrophilic groups and lipophilic groups; the weight-average molecular weight of the oligomers is 300-5000; the hydrophilic groups include amide groups and / or carboxyl groups.

[0010] In the present invention, the molecular structure of the oligomers contains hydrophilic groups and lipophilic groups, has a molecular structure similar to that of an emulsifier, can play the role of an emulsifier, ensure the stable synthesis of the soap-free polymer agglomerant, and has good long-term stability; when used for agglomerating polybutadiene latex, it has good agglomeration effect and can obtain polybutadiene latex with large particle size and good stability; moreover, since no external emulsifier is added, when preparing ABS resin with the agglomerated polybutadiene latex as the raw material, the performance of the ABS resin will not be affected by excessive emulsifier, and the obtained ABS resin has better impact resistance and lower yellowness index, and is more beautiful.

[0011] In the present invention, the soap-free polymer agglomerant means that the preparation raw materials of the polymer agglomerant do not include an emulsifier.

[0012] In the present invention, the weight-average molecular weight of the oligomers is 300-5000, for example, it can be 300, 500, 600, 800, 1000, 1200, 1400, 1600, 1800, 2000, 2200, 2400, 2600, 2800, 3000, 3200, 3400, 3600, 3800, 4000, 4200, 4400, 4600, 4800, 5000 or the range between any of the above values; more preferably 400-3500, and further preferably 405-1950.

[0013] In the present invention, the weight-average molecular weight of the oligomer and the number-average molecular weight of the soap-free polymer agglomerating agent are obtained by testing with a gel permeation chromatograph. Specifically: tetrahydrofuran is selected as the mobile phase, the sample concentration is 4 mg / ml, and the injection volume is 10 μL. The specific test standard refers to GB / T 27843-2011 "Determination of Low Molecular Weight Components in Chemical Polymer - Gel Permeation Chromatography (GPC)". The weight-average molecular weight of the oligomer within the above range can provide a good self-emulsifying effect, and then be used for agglomerating polybutadiene latex, with a good agglomerating effect, and large-particle-size polybutadiene latex can be obtained. Moreover, the ABS resin prepared from the agglomerated polybutadiene latex as the raw material has better impact resistance and a lower yellow index, and is more aesthetically pleasing. If the weight-average molecular weight is too high or too low, the self-emulsifying effect will become poor or even lost, affecting the performance of the soap-free polymer agglomerating agent, and further affecting the impact resistance and yellowing resistance of the finally obtained ABS resin.

[0014] Preferably, the lipophilic group includes an ester group.

[0015] Preferably, the mass percentage content of the oligomer in the soap-free polymer agglomerating agent is ≤ 10%, for example, it can be 0.1%, 0.2%, 0.5%, 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9%, 10% or the range between any of the above values; more preferably, it is 3.5 - 7%.

[0016] In the present invention, the oligomer comprises at least one compound having the structure shown in Formula I and / or at least one polymer having the structure shown in Formula II:

[0017]

[0018] Among them, in Formula I, R 1 , R 2 are each independently selected from H or a C1 - C10 straight-chain or branched-chain alkyl group; R 3 is selected from H, a C1 - C10 straight-chain or branched-chain alkyl group, or at least one of -(CH 2 )n 11 -COOH; R 4 is selected from any one of -(CH 2 )n 21 -CONR N1 R N2 , -N(R N3 )CO-R 7 or -COOH; n 1 , n 2 , n 11 , n 21 are each independently selected from integers greater than or equal to 0; R N1 , R N2, R N3 , R 7 Each independently selected from H or a C1-C10 linear or branched alkyl group.

[0019] In formula II, R 1 , R 2 Each independently selected from H or a C1-C10 linear or branched alkyl group; R 3 , R 5 Each independently selected from H, a C1-C10 linear or branched alkyl group, or at least one of -(CH 2 )n 12 -COOH;

[0020] R 4 , R 6 Each independently selected from -(CH 2 )n 22 -CONR N1 R N2 , -N(R N3 )CO-R 7 or -COOH; and one of R 4 , R 6 is selected from -COOH; n 1 , n 2 , n 3 , n 12 , n 22 Each independently selected from integers greater than or equal to 0; R N1 , R N2 , R N3 , R 7 Each independently selected from H or a C1-C10 linear or branched alkyl group.

[0021] In the present invention, the oligomer is an oligomer formed during the preparation of the soap-free polymer agglomerant. By adjusting the monomer dosage, type, and preparation process (including the addition sequence, addition ratio, reaction temperature, and time of the monomer in the preparation process, etc.), the molecular structure, weight-average molecular weight, and mass percentage content of the oligomer in the soap-free polymer agglomerant can be adjusted.

[0022] In the present invention, the preparation raw materials of the soap-free polymer agglomerant include monomers and initiators; the monomers include hydrophilic monomers and lipophilic monomers; the mass of the initiator is 0.1-5% of the total mass of the monomers, preferably 0.2-3%, and more preferably 0.5-2.5%.

[0023] In the present invention, the molar ratio of the hydrophilic monomer to the lipophilic monomer is (0.05 - 0.8):1, where the specific values in (0.05 - 0.8) can be, for example, 0.05, 0.06, 0.08, 0.1, 0.12, 0.14, 0.16, 0.18, 0.2, 0.22, 0.24, 0.26, 0.28, 0.3, 0.32, 0.34, 0.36, 0.38, 0.4, 0.42, 0.44, 0.46, 0.48, 0.5, 0.52, 0.55, 0.58, 0.6, 0.62, 0.65, 0.68, 0.7, 0.72, 0.75, 0.78 or the ranges between any of the above values; more preferably, the molar ratio of the hydrophilic monomer to the ester monomer is (0.09 - 0.55):1.

[0024] Preferably, the hydrophilic monomer includes an amide monomer and / or a carboxyl-containing monomer.

[0025] Preferably, the amide monomer includes at least one of acrylamide, N-tert-butylacrylamide, erucic acid amide, oleic acid amide, and N-methyl-N-vinylacetamide.

[0026] Preferably, the carboxyl-containing monomer includes at least one of (meth)acrylic acid, itaconic acid, and fumaric acid.

[0027] Preferably, the lipophilic monomer includes (meth)acrylic acid alkyl ester and / or vinyl acetate.

[0028] Preferably, the (meth)acrylic acid alkyl ester includes at least one of methyl methacrylate, n-butyl acrylate, butyl methacrylate, isooctyl acrylate, ethyl acrylate, and tert-butyl acrylate.

[0029] Preferably, the initiator includes at least one of inorganic peroxide initiators, azo initiators, and organic peroxide initiators.

[0030] In the present invention, the inorganic peroxide initiators include at least one of potassium persulfate, ammonium persulfate, hydrogen peroxide, and sodium persulfate; the azo initiators include at least one of azodiisobutylamidine hydrochloride, azodiisobutimidazoline hydrochloride, azodicyanovaleric acid, azodiisopropylimidazoline, azodiisobutyronitrile, azodiisooctanenitrile, and dimethyl azodiisobutyrate; the organic peroxide initiators include cumene hydroperoxide and / or benzoyl peroxide.

[0031] Preferably, the preparation raw materials further include a crosslinking agent.

[0032] Preferably, the mass of the crosslinking agent is 3-17% of the total mass of the monomers, for example, it can be 3%, 3.1%, 3.2%, 3.3%, 3.4%, 3.5%, 3.8%, 4%, 4.5%, 5%, 5.5%, 6%, 6.5%, 7%, 7.5%, 8%, 8.5%, 9%, 9.5%, 10%, 11%, 12%, 13%, 14%, 15%, 16%, 17% or the range between any of the above values; more preferably, it is 3.5-12%.

[0033] Preferably, the crosslinking agent includes at least one of 1,4-butanediol diacrylate, ethylene glycol dimethacrylate, p-toluenesulfonic acid, p-toluenesulfonyl chloride, and divinylbenzene.

[0034] Preferably, the gel content of the soap-free polymer agglomerant is 34-92%, for example, it can be 34%, 36%, 38%, 40%, 42%, 44%, 46%, 48%, 50%, 52%, 54%, 56%, 58%, 60%, 62%, 64%, 66%, 68%, 70%, 72%, 74%, 76%, 78%, 80%, 82%, 84%, 86%, 88%, 90%, 92% or the range between any of the above values; more preferably, the gel content is 50-89%.

[0035] Preferably, the preparation raw materials further include a chain transfer agent, and the mass of the chain transfer agent is 0.1-3% of the total mass of the monomers, preferably 0.2-2.5%, and more preferably 0.5-1.5%.

[0036] In the present invention, the chain transfer agent includes at least one of dodecyl mercaptan, mercaptoacetic acid, mercaptopropionic acid, sodium bisulfite, mercaptoethanol, mercaptopropanol, formic acid, and sodium hypophosphite.

[0037] Preferably, the number-average molecular weight of the soap-free polymer agglomerant is 10,000-55,000, for example, it can be 10,000, 15,000, 20,000, 25,000, 30,000, 35,000, 40,000, 45,000, 50,000, 52,000, 54,000 or the range between any of the above values.

[0038] Preferably, the soap-free polymer agglomerant has a core-shell structure.

[0039] In the present invention, in the core-shell structure of the soap-free polymer agglomerant, the core is a polymer inner core formed by ester monomers; the shell is a polymer outer shell formed by hydrophilic monomers.

[0040] In the present invention, the solid content of the soap-free polymer agglomerant is 28-50%.

[0041] Second aspect, the present invention provides a preparation method of the soap-free polymer agglomerating agent described in the first aspect, and the preparation method includes the following steps:

[0042] Mix a hydrophilic monomer, a lipophilic monomer, an initiator and a solvent, and react to obtain the soap-free polymer agglomerating agent.

[0043] In the present invention, during the reaction process of the preparation method, oligomers can be formed. The molecular structure of the oligomers contains hydrophilic groups and lipophilic groups, so that the oligomers have self-emulsifying properties. Without adding an emulsifier, the surface activity of the oligomers can be used for emulsion polymerization to ensure the progress of the polymerization reaction, and at the same time, the stability of the obtained agglomerating agent latex is good; when used to agglomerate polybutadiene latex and using the agglomerated polybutadiene latex as a raw material to prepare ABS resin, it can avoid the problem that the impact resistance and yellowing resistance of ABS resin become poor due to the introduction of too much externally added emulsifier.

[0044] In the present invention, the solvent includes water; in terms of parts by weight, the mass of the solvent can be 25 to 200 parts, for example, it can be 25 parts, 50 parts, 75 parts, 100 parts, 125 parts, 150 parts, 175 parts, 195 parts or the range between any of the above values; the mass of the solvent only needs to make the solid content of the soap-free polymer agglomerating agent be 28 to 50%.

[0045] Preferably, the mixed raw materials further include a crosslinking agent and / or a chain transfer agent.

[0046] Preferably, the reaction includes the following steps:

[0047] S1: Mix 1 to 95% (for example, it can be 1%, 5%, 9%, 10%, 20%, 30%, 40%, 50%, 60%, 70%, 80%, 90%, 95% or the range between any of the above values) of the hydrophilic monomer based on the total mass of the hydrophilic monomer and 5 to 30% (for example, it can be 5%, 9%, 10%, 15%, 20%, 25%, 30% or the range between any of the above values) of the lipophilic monomer based on the total mass of the lipophilic monomer to obtain a mixed monomer; then mix the mixed monomer, 9 to 99.8% of the initiator in the formula amount (for example, it can be 9%, 10%, 20%, 30%, 40%, 50%, 60%, 70%, 80%, 90%, 95%, 99% or the range between any of the above values), the solvent and the optional chain transfer agent, and react to obtain product A; S2: Mix product A obtained in step S1 with 6 to 55% of the lipophilic monomer (for example, it can be 6%, 8%, 10%, 15%, 20%, 25%, 30%, 35%, 40%, 45%, 50%, 54% or the range between any of the above values) of the lipophilic monomer and the remaining initiator, and react to obtain product B;

[0048] S3: Mix the remaining hydrophilic monomers and the remaining lipophilic monomers to obtain a mixed monomer; then mix the product B obtained in step S2 with the mixed monomer and an optional crosslinking agent, and react to obtain the soap-free polymer agglomerating agent.

[0049] In the present invention, the types of monomers added in steps S1, S2, and S3 are different. Among them, hydrophilic monomers and lipophilic monomers are added in S1 and S3, and only lipophilic monomers are added in S2. The added mass is calculated based on the total mass of each monomer being 100%. The reason is that: in the initial stage of the reaction, that is, in the S1 stage, an oligomer with surface activity needs to be obtained to provide emulsion polymerization stability; in the middle stage of the reaction, that is, in the S2 stage, it is the growth period of the particle size of the polymer agglomerating agent emulsion. The hydrophobic ester monomer can diffuse into the micelles and continuously polymerize to increase the particle size; in the later stage of the reaction, that is, in the S3 stage, as the particle size of the polymer agglomerating agent latex particles increases, the content of the original oligomer is not sufficient to maintain the emulsion stability, and new oligomers with surface activity need to be added to maintain the emulsion stability.

[0050] Preferably, the molar ratio of the hydrophilic monomer to the ester monomer in the mixed monomer in step S1 is (0.03 - 2.7):1. Among them, the specific values in (0.03 - 2.7) can be, for example, 0.03, 0.04, 0.05, 0.06, 0.08, 0.1, 0.12, 0.15, 0.18, 0.2, 0.22, 0.25, 0.28, 0.3, 0.32, 0.35, 0.38, 0.4, 0.42, 0.45, 0.48, 0.5, 0.52, 0.55, 0.58, 0.6, 0.62, 0.65, 0.68, 0.7, 0.72, 0.75, 0.78, 0.8, 0.82, 0.85, 0.88, 0.9, 0.92, 0.95, 0.98, 1, 1.1, 1.2, 1.3, 1.4, 1.45, 1.48, 1.5, 1.55, 1.6, 1.65, 1.7, 1.75, 1.8, 2, 2.2, 2.4, 2.6 or the range between any of the above values; more preferably, the molar ratio is (0.2 - 1.2):1.

[0051] In the present invention, the solvent in step S1 includes water; calculated by weight, the mass of the solvent is 25 - 200 parts, for example, it can be 25 parts, 50 parts, 75 parts, 100 parts, 125 parts, 150 parts, 175 parts, 195 parts or the range between any of the above values.

[0052] Preferably, the reaction in step S1 is carried out in the presence of a protective atmosphere.

[0053] In the present invention, the protective atmosphere includes but is not limited to nitrogen.

[0054] Preferably, the temperature of the reaction in step S1 is 50 to 83 °C, for example, it can be 50 °C, 52 °C, 55 °C, 58 °C, 60 °C, 62 °C, 65 °C, 68 °C, 70 °C, 72 °C, 75 °C, 78 °C, 80 °C, 82 °C, 83 °C or the range between any of the above values; the rotation speed is 120 to 200 rpm, for example, it can be 120 rpm, 140 rpm, 160 rpm, 180 rpm, 200 rpm or the range between any of the above values; the time is 10 to 120 min, for example, it can be 10 min, 20 min, 30 min, 40 min, 50 min, 60 min, 70 min, 80 min, 90 min, 100 min, 110 min, 120 min or the range between any of the above values.

[0055] Preferably, the temperature of the reaction in step S2 is 55 to 85 °C, for example, it can be 55 °C, 56 °C, 58 °C, 60 °C, 62 °C, 64 °C, 66 °C, 68 °C, 70 °C, 72 °C, 74 °C, 76 °C, 78 °C, 80 °C, 82 °C, 84 °C, 85 °C or the range between any of the above values; the time is 30 to 85 min, for example, it can be 30 min, 32 min, 35 min, 38 min, 40 min, 42 min, 45 min, 48 min, 50 min, 52 min, 55 min, 58 min, 60 min, 62 min, 65 min, 68 min, 70 min, 72 min, 75 min, 78 min, 80 min, 82 min, 85 min or the range between any of the above values.

[0056] Preferably, the molar ratio of the hydrophilic monomer to the lipophilic monomer in the mixed monomers in step S3 is (0.03 to 1.82):1, where the specific values in (0.03 to 1.82) can be, for example, 0.03, 0.04, 0.05, 0.06, 0.08, 0.1, 0.12, 0.15, 0.18, 0.2, 0.22, 0.25, 0.28, 0.3, 0.32, 0.35, 0.38, 0.4, 0.42, 0.45, 0.48, 0.5, 0.52, 0.55, 0.58, 0.6, 0.62, 0.65, 0.68, 0.7, 0.72, 0.75, 0.78, 0.8, 0.82, 0.85, 0.88, 0.9, 0.92, 0.95, 0.98, 1, 1.1, 1.15, 1.18, 1.2, 1.4, 1.6, 1.8 or the range between any of the above values; more preferably, the molar ratio is (0.12 to 0.9):1.

[0057] Preferably, the method for adding the mixed monomers in step S3 includes dropwise addition, and the time for the dropwise addition is 40 to 200 min, for example, it can be 40 min, 45 min, 50 min, 55 min, 60 min, 65 min, 70 min, 75 min, 80 min, 85 min, 90 min, 95 min, 100 min, 105 min, 110 min, 115 min, 120 min, 125 min, 130 min, 135 min, 140 min, 145 min, 150 min, 155 min, 160 min, 165 min, 170 min, 175 min, 180 min, 185 min, 190 min, 195 min, 200 min or the range between any of the above values.

[0058] Preferably, the temperature of the reaction in step S3 is 70 to 87 °C, for example, it can be 70 °C, 72 °C, 74 °C, 76 °C, 78 °C, 80 °C, 82 °C, 84 °C, 85 °C, 86 °C or the range between any of the above values; the time is 25 to 180 min, for example, it can be 30 min, 35 min, 40 min, 45 min, 50 min, 55 min, 60 min, 65 min, 70 min, 75 min, 80 min, 85 min, 90 min, 95 min, 100 min, 105 min, 110 min, 115 min, 120 min, 125 min, 130 min, 135 min, 140 min, 145 min, 150 min, 155 min, 160 min, 165 min, 170 min, 175 min, 180 min or the range between any of the above values.

[0059] As a preferred technical solution of the present invention, the preparation method includes the following steps:

[0060] S1: Mix 1 to 95% of the hydrophilic monomers by total mass of the hydrophilic monomers and 5 to 30% of the lipophilic monomers by total mass of the lipophilic monomers to obtain mixed monomers; then mix the mixed monomers, 9 to 99.8% of the initiator in the formula amount, 25 to 200 parts of the solvent and an optional chain transfer agent to obtain a mixed solution with a mass concentration of 2 to 50%; then under nitrogen protection, react at a high shear rotation speed of 120 to 200 rpm and a temperature of 50 to 83 °C for 10 to 120 min to obtain product A;

[0061] S2: Add 6 to 55% of the lipophilic monomers by total mass of the lipophilic monomers and the remaining initiator to product A obtained in step S1, raise the temperature to 55 to 85 °C, and react for 30 to 85 min to obtain product B;

[0062] S3: Mix the remaining hydrophilic monomers and the remaining lipophilic monomers to obtain a mixed monomer; then dropwise add the mixed monomer and an optional crosslinking agent to the product B obtained in step S2, control the dropping time of the monomer to be 40 - 200 min, raise the temperature to 70 - 87 °C, and react for 25 - 180 min to obtain the soap-free polymer agglomerating agent.

[0063] In a third aspect, the present invention provides an agglomerated polybutadiene, which comprises a base polybutadiene and an agglomerating agent; the agglomerating agent comprises the soap-free polymer agglomerating agent described in the first aspect.

[0064] Preferably, based on 100 parts by dry weight of the base polybutadiene, the added mass of the dry base of the soap-free polymer agglomerating agent is 0.1 - 20 parts, for example, it can be 0.1 part, 0.5 part, 1 part, 2 parts, 3 parts, 4 parts, 5 parts, 6 parts, 7 parts, 8 parts, 9 parts, 10 parts, 11 parts, 12 parts, 13 parts, 14 parts, 15 parts, 16 parts, 17 parts, 18 parts, 19 parts, 20 parts or the range between any of the above values; more preferably 1.5 - 10.5 parts.

[0065] Preferably, the ratio of the D50 particle size of the agglomerated polybutadiene to the D50 particle size of the base polybutadiene ≥ 2, more preferably the ratio ≥ 3, and particularly preferably 3.2 - 8.

[0066] In the present invention, the D50 particle size of the base polybutadiene is 50 - 150 nm; the D50 particle size of the agglomerated polybutadiene is 200 - 800 nm; more preferably, the D50 particle size of the base polybutadiene is 50 - 120 nm; the D50 particle size of the agglomerated polybutadiene is 250 - 800 nm.

[0067] In the present invention, the agglomerated polybutadiene can be prepared by a conventional method. Exemplarily, the preparation method includes: mixing a base polybutadiene emulsion (D50 particle size is 100 nm), the soap-free polymer agglomerating agent and a solvent (including deionized water) according to the formula amount, and stirring at 25 °C - 50 °C and 40 - 100 rpm for 100 - 150 min to obtain the agglomerated polybutadiene.

[0068] In the present invention, the basic polybutadiene emulsion can be obtained by purchasing from the market or prepared by conventional methods. Exemplarily, the preparation method includes: mixing 100 parts of butadiene, 0.5 - 6 parts of initiator, 0.1 - 1 part of electrolyte, 1 - 6 parts of emulsifier, 0.1 - 0.5 part of chain transfer agent with 150 - 250 parts of solvent uniformly, heating to 60 - 80 °C, and starting the polymerization reaction. During the reaction process, samples are taken. When the monomer conversion rate tested by the drying method is ≥90%, the reaction reaches the end point, and the basic polybutadiene emulsion is obtained. The initiator, electrolyte, emulsifier, and chain transfer agent can adopt conventional auxiliaries in the art. For example, the initiator includes but is not limited to potassium persulfate, ammonium persulfate, azobisisobutyronitrile, azobisisoheptonitrile, dimethyl azobisisobutyrate, cumene hydroperoxide, benzoyl peroxide, etc. A redox initiator system can also be adopted, and a reducing agent such as ferrous sulfate, ferric chloride, sodium formaldehyde sulfoxylate, etc. is added. The electrolyte includes but is not limited to potassium carbonate. The emulsifier includes but is not limited to rosin potassium soap, potassium oleate, alkylphenol polyoxyethylene ether, etc. The chain transfer agent includes but is not limited to dodecyl mercaptan, mercaptoacetic acid, mercaptopropionic acid, sodium bisulfite, formic acid, etc.

[0069] Fourthly, the present invention provides an ABS resin, and the preparation raw materials of the ABS resin include the agglomerated polybutadiene described in the second aspect.

[0070] In the present invention, the preparation raw materials of the ABS resin further include comonomers, initiators, emulsifiers, and chain transfer agents. Based on 100 parts of the dry basis of the agglomerated polybutadiene, the dosage of the comonomer is 20 - 150 parts, for example, it can be 20 parts, 30 parts, 40 parts, 50 parts, 60 parts, 70 parts, 80 parts, 90 parts, 100 parts, 110 parts, 120 parts, 130 parts, 140 parts, 150 parts or the range between any of the above values; the dosage of the initiator is 0.5 - 25 parts, for example, it can be 0.5 part, 1 part, 2 parts, 4 parts, 6 parts, 8 parts, 10 parts, 12 parts, 14 parts, 16 parts, 18 parts, 20 parts, 22 parts, 24 parts, 25 parts or the range between any of the above values; the dosage of the emulsifier is 4.5 - 15.5 parts, for example, it can be 4.5 parts, 5 parts, 6 parts, 8 parts, 10 parts, 12 parts, 14 parts, 15 parts or the range between any of the above values; the dosage of the chain transfer agent is 1 - 6 parts, for example, it can be 1 part, 2 parts, 3 parts, 4 parts, 5 parts, 6 parts or the range between any of the above values.

[0071] In the present invention, the comonomers include aromatic vinyl monomers and vinyl cyanide monomers. The mass percentage content of the aromatic vinyl monomers in the comonomers is 60 - 90%, for example, it can be 60%, 65%, 70%, 75%, 80%, 85%, 90% or the range between any of the above values.

[0072] In the present invention, among the raw materials for preparing the ABS resin, the aromatic vinyl monomers include, but are not limited to, styrene, and the vinyl cyanide monomers include, but are not limited to, acrylonitrile, methacrylonitrile, etc.; in addition, there are no special restrictions on the types of initiators, emulsifiers, and chain transfer agents, and conventional auxiliaries in the art can be used; for example, the initiators include, but are not limited to, potassium persulfate, ammonium persulfate, azobisisobutyronitrile, azobisisoheptonitrile, dimethyl azobisisobutyrate, cumene hydroperoxide, benzoyl peroxide, etc.; a redox initiation system can also be used, and a reducing agent such as ferrous sulfate, ferric chloride, sodium formaldehyde sulfoxylate, etc. can be added; the emulsifiers include, but are not limited to, potassium rosinate, potassium oleate, alkylphenol polyoxyethylene ether, etc.; the chain transfer agents include, but are not limited to, dodecyl mercaptan, mercaptoacetic acid, mercaptopropionic acid, sodium bisulfite, formic acid, etc.

[0073] In the present invention, the preparation method of the ABS resin can be prepared by a conventional method. Exemplarily, the preparation method includes: mixing the agglomerated polybutadiene with comonomers, initiators, emulsifiers, chain transfer agents, and solvents, reacting at 40 - 80 °C for 2 - 8 h to obtain an ABS graft latex; then mixing the graft latex with a coagulant and a solvent, coagulating at 70 - 100 °C for 1 - 3 h, and then coagulating at 80 - 110 °C for 0.5 - 2.5 h, washing and drying to obtain the ABS resin.

[0074] In the present invention, based on 100 parts by mass of the ABS graft latex, the dosage of the coagulant is 5 - 15 parts, for example, it can be 5 parts, 6 parts, 8 parts, 10 parts, 12 parts, 14 parts, 15 parts, or the range between any of the above values; the mass of the solvent is 300 - 700 parts, for example, it can be 300 parts, 350 parts, 400 parts, 450 parts, 500 parts, 550 parts, 600 parts, 650 parts, 700 parts, or the range between any of the above values; the solvent includes water.

[0075] Preferably, the yellowness index of the ABS resin ≤ 18, more preferably the yellowness index ≤ 16.5, and particularly preferably the yellowness index ≤ 15.

[0076] Preferably, the notched Izod impact strength of the ABS resin ≥ 10 KJ·m -2 , more preferably the notched Izod impact strength ≥ 15 KJ·m -2 , particularly preferably the notched Izod impact strength ≥ 20 KJ·m -2 .

[0077] The numerical ranges described in the present invention not only include the above - listed point values, but also include any point values between the above - mentioned numerical ranges that are not listed. Due to space limitations and for the sake of brevity, the present invention does not exhaustively list the specific point values included in the ranges.

[0078] Compared with the prior art, the beneficial effects of the present invention are as follows:

[0079] The soap-free polymer agglomerating agent provided by the present invention does not contain emulsifiers and comprises oligomers having hydrophilic groups and lipophilic groups, which can provide self-emulsifying properties and ensure the stability of the agglomerating agent. When used for agglomerating polybutadiene latex, it not only has a good agglomeration effect and can obtain polybutadiene latex with large particle sizes, but also, when preparing ABS resin from the agglomerated polybutadiene latex as a raw material, the obtained ABS resin has better impact resistance and lower yellowness index, making it more aesthetically pleasing. Detailed Embodiments

[0080] The technical solutions of the present invention will be further described below through specific embodiments. Those skilled in the art should understand that the described embodiments are only for helping to understand the present invention and should not be regarded as specific limitations on the present invention.

[0081] All the materials used in the embodiments and comparative examples of the present invention can be obtained through commercial purchase or prepared by conventional methods. Unless otherwise specified, the materials used in the present invention are sourced from commercial suppliers.

[0082] In the present invention, the test method for the gel content includes: referring to the industry standard: SH / T 1050 - 2014, "Determination of Gel Content of Synthetic Raw Rubber". The specific method is as follows: Spread the obtained soap-free polymer agglomerating agent emulsion on a smooth flat plate to obtain a film with a thickness of 0.2 mm to 0.7 mm. After natural air drying and no flow, place it in a forced-air oven and dry it at 80 °C for 2 h. Then remove the film from the flat plate, place it in a desiccator for 5 - 10 min to restore to room temperature. Take 0.25 g ± 0.0050 g of the film, denoted as m, accurate to 0.0001 g, and put it into a pre-weighed filter (made of 120-mesh stainless steel screen), and place the filter in a 200 mL beaker. Add approximately 50 ml of toluene to the beaker to ensure that the sample is completely immersed in toluene. Seal the beaker with plastic wrap and tin foil, place it in a fume hood away from light, and dissolve it at 23 ± 5 °C for 16 h to 24 h. After complete dissolution, use tweezers to take out the filter from the beaker, and use a pipette to suck an appropriate amount of toluene to rinse the filter and the gel therein to wash away the sol remaining on the filter, rinsing 4 times. Then place the filter on an enamel tray lined with clean filter paper or wire mesh, place it in a fume hood for ventilation for 2 h, and then dry the filter in an oven at 100 °C ± 2 °C for 1 h. Take it out and place it in a desiccator for 5 - 10 min, then weigh and record, and then put it back into the oven to dry for 30 min. Take it out, cool and dry, and then weigh and record again. Repeat this step until the difference between the two weighings ≤ 0.3 mg.

[0083] The formula for calculating the gel content is:

[0084]

[0085] Wherein:

[0086] m 2 — Mass (after drying) of the polymer insoluble in toluene and the sieve, g;

[0087] m 1 — Mass of the sieve, g;

[0088] m — Mass of the sample, g.

[0089] The D50 particle size is obtained by testing with a laser nano particle size analyzer. Specifically: Using deionized water as the solvent, dilute the sample to a mass concentration of about 0.01%, add it to the middle of the sample cell, and then conduct the test on the machine; The number average molecular weight, weight average molecular weight, and mass percentage content of oligomers can be obtained by testing with gel permeation chromatography. The specific method is as follows:

[0090] The mobile phase is tetrahydrofuran, the test temperature is 40 °C, the flow rate is 0.5 mL / min, the standard sample is polystyrene, and the chromatographic column model is pl-mixed-c; Take about 1 g of the soap-free polymer agglomerator and place it in a weighing bottle. After drying at 120 °C for 30 min, dissolve the dried film in tetrahydrofuran at a concentration of 4 mg / ml, and filter it through a microporous filter into the injection bottle, then the number average molecular weight and weight average molecular weight of the soap-free polymer agglomerator and its oligomers can be tested. For the obtained GPC test curve, conduct peak area integration. The ratio of the peak area of the oligomer, i.e., the low molecular weight peak, to the total spectrum peak area is the mass percentage content of the oligomer.

[0091] Example 1

[0092] This example provides a soap-free polymer agglomerator. Calculated by weight, the raw materials for preparing the soap-free polymer agglomerator include monomers, divinylbenzene as a cross-linking agent accounting for 5.5% of the total mass of the monomers, azobisisobutyronitrile as an initiator accounting for 0.44% of the total mass of the monomers, and mercaptopropionic acid as a chain transfer agent accounting for 0.55% of the total mass of the monomers; The monomers include hydrophilic monomer fumaric acid and lipophilic monomer ethyl acrylate with a molar ratio of 0.1:1.

[0093] This example provides a preparation method of the soap-free polymer agglomerator, which specifically includes the following steps:

[0094] S1: Mix 40.8% of the total mass of the hydrophilic monomer fumaric acid and 18.5% of the total mass of the lipophilic monomer ethyl acrylate to obtain a mixed monomer with a molar ratio of fumaric acid to ethyl acrylate of 0.23:1. Then mix the mixed monomer, 50% of the formula amount of the initiator, the chain transfer agent, and water in a reaction flask. After displacing with nitrogen three times, start stirring and quickly heat up to 60 °C, and react for 120 min under the insulation condition to obtain product A;

[0095] S2: Add ethyl acrylate monomer accounting for 34.6% of the total mass of the lipophilic monomers and the remaining initiator to Product A obtained in Step S1, heat up to 75 °C, and react for 60 min to obtain Product B;

[0096] S3: Supplement the crosslinking agent to Product B obtained in Step S2, and dropwise add the remaining monomers, that is, a mixed monomer with a molar ratio of fumaric acid to ethyl acrylate of 0.13:1. Control the dropping time to be 180 min, heat up to 82 °C, and react for 30 min to obtain the soap-free polymer agglomerant with a solid content of 45 ± 1%.

[0097] Examples 2 to 18 respectively provide a soap-free polymer agglomerant, the difference from Example 1 is only that the types and amounts of each raw material, and the percentage content of the hydrophilic monomers added in Steps S1 and S3, the percentage content of the lipophilic monomers added in Step S2, and the molar ratio of the hydrophilic monomers to the lipophilic monomers in the mixed monomers in Steps S1 and S3 in the preparation method are different; the specific parameters are shown in Tables 1 to 3; others are the same as in Example 1.

[0098] The number-average molecular weight, weight-average molecular weight of the oligomer, and mass percentage content of the oligomer of the soap-free polymer agglomerants provided in Examples 1 to 18 are shown in Tables 1 to 3; among them, the numerical values corresponding to the hydrophilic monomers and lipophilic monomers represent the molar ratio of the two; for example, in Example 1, the hydrophilic monomer is 0.1 and the lipophilic monomer is 1, indicating that the molar ratio of the hydrophilic monomer to the lipophilic monomer is 0.1:1; " / " means that this raw material is not included.

[0099] Among them, in the preparation method of Example 18, the monomer addition order is different, that is, in S1, add ethyl acrylate accounting for 34.6% of the total mass of the lipophilic monomers, and in S2, add the mixed monomer, and the mixed monomer is: mix fumaric acid accounting for 40.8% of the total mass of the hydrophilic monomers and ethyl acrylate accounting for 18.5% of the total mass of the lipophilic monomers to obtain a mixed monomer with a molar ratio of fumaric acid to ethyl acrylate of 0.23:1; other raw materials, amounts, and step parameters are the same as in Example 1.

[0100] Table 1

[0101]

[0102] Table 2

[0103]

[0104]

[0105] Table 3

[0106]

[0107]

[0108] Comparative Example 1

[0109] This comparative example provides a polymer agglomerant, the difference from Example 1 being that the preparation raw materials further include oleate (with a mass of 5.7% of the total mass of the hydrophilic monomer and the lipophilic monomer). In the preparation method, the raw materials mixed in step S1 further include oleate, and the other raw materials, dosages, and step parameters are the same as those in Example 1.

[0110] Comparative Example 2

[0111] This comparative example provides a soap-free polymer agglomerant, the difference from Example 1 being that the total mass of the monomers remains unchanged, and the monomer is dimethylaminoethyl methacrylate, so that the hydrophilic groups in the oligomers of the obtained soap-free polymer agglomerant are not amide groups and / or carboxyl groups. The preparation method includes: mixing dimethylaminoethyl methacrylate with an initiator, a crosslinking agent, a chain transfer agent, and a solvent, and reacting at 70 °C for 3 h to obtain the soap-free polymer agglomerant.

[0112] Application Example 1

[0113] An agglomerated polybutadiene, the agglomerated polybutadiene being an agglomerated polybutadiene latex, including a basic polybutadiene latex (D50 particle size is 100 nm) and an agglomerant; the agglomerants are the polymer agglomerants provided in Examples 1 to 18 and Comparative Examples 1 to 2 respectively; the D50 particle size, the type and dosage of the agglomerant (based on 100 parts of the dry basis of the basic polybutadiene latex) of the agglomerated polybutadiene latex are shown in Table 4.

[0114] The preparation method of the basic polybutadiene latex is as follows: Add 100 parts of butadiene, 1.5 parts of potassium persulfate, 1.5 parts of cumene hydroperoxide, 0.5 part of potassium carbonate, 3 parts of rosin potassium soap, 0.3 part of dodecyl mercaptan, and 200 parts of deionized water into a reactor, mix evenly, heat up to 68 °C, and start the polymerization reaction. During the reaction process, samples are taken, and when the monomer conversion rate is tested to be 90% by the drying method, the reaction reaches the end point, that is, the basic polybutadiene latex is obtained.

[0115] The preparation method of the agglomerated polybutadiene includes: taking 100 mass parts of the basic polybutadiene latex (D50 particle size is 100 nm) in terms of dry basis, and a certain mass part (the number of parts of the agglomerant shown in Table 4) of the soap-free polymer agglomerant (prepared in the example), 50 parts of deionized water, putting them into a reaction kettle, starting stirring, and ending after low-speed stirring (80 rpm) for 120 min to obtain the agglomerated polybutadiene.

[0116] Table 4

[0117]

[0118]

[0119] As can be seen from Table 4, the soap-free polymer agglomerating agent provided by the present invention has good agglomeration effect, and can agglomerate the base polybutadiene latex with a D50 particle size of 100 nm to obtain an agglomerated polybutadiene with a D50 particle size of 330 - 620 nm; while the agglomerating agents provided in Comparative Examples 1 and 2 have poor agglomeration effect, and the D50 particle size of the agglomerated polybutadiene is smaller.

[0120] Application Example 2

[0121] An ABS resin, the preparation method of the ABS resin comprising:

[0122] (1) Adding a butadiene-based polymer emulsion into a reaction kettle, and then based on 100 parts of the dry basis of the butadiene-based polymer emulsion, adding 0.015 part of ferric sulfate, 3 parts of sodium formaldehyde sulfoxylate, uniformly stirring, heating the reaction kettle to 67°C, and adding 2.51 parts of cumene hydroperoxide, 75 parts of styrene, 25 parts of acrylonitrile, 1.5 parts of tert-dodecyl mercaptan, 5 parts of sodium dodecyl sulfonate, and 175 parts of deionized water, continuously dropping for 2 h, and continuing to react for 5 h after heating is completed to obtain an ABS graft latex.

[0123] (2) Mixing 100 parts of the ABS graft latex obtained in step (1) with 500 parts of deionized water and 10 parts of magnesium sulfate, starting stirring and heating to 85°C, stirring for 2 h, then raising the temperature to 95°C, continuing to stir for 1.5 h, washing the above suspension with deionized water for multiple times, and then drying to obtain the ABS resin after constant weight, that is, obtaining ABS rubber powder.

[0124] Wherein, the butadiene-based polymer emulsion in step (1) is respectively the agglomerated polybutadiene latexes provided by Nos. 1 - 24 in Application Example 1.

[0125] Performance test

[0126] (1) Izod impact strength with notched specimen: Test according to the standard GB / T 1843-2008, "Plastics - Determination of Izod impact strength".

[0127] (2) Yellowness index: Test according to the standard GB / T 39822-2021, "Plastics - Determination of yellowness index and its change value".

[0128] The specific test results are shown in Table 5.

[0129] Table 5

[0130]

[0131]

[0132] As can be seen from Table 5, the ABS resin prepared from the polybutadiene latex agglomerated with the soap-free polymer agglomerant provided by the present invention has high impact strength and a small yellow index; the Izod notched impact strength of the ABS resin is ≥ 10.8 kJ / m 2 , and the yellow index is ≤ 18; it can even reach an Izod notched impact strength of ≥ 20.2 kJ / m 2 , and the yellow index is ≤ 15.

[0133] As can be seen from the comparative examples, for the ABS resin obtained with an agglomerant other than the specific agglomerant of the present invention, the impact resistance is poor, the yellow index is high, and the color aesthetic performance is poor.

[0134] The specific embodiments described above further elaborate on the purpose, technical solutions, and beneficial effects of the present invention. It should be understood that the above are only specific embodiments of the present invention and are not used to limit the present invention. Any modifications, equivalent replacements, improvements, etc. made within the spirit and principles of the present invention shall be included within the protection scope of the present invention.

Claims

1. A soap-free polymer agglomerating agent, characterized in that: The soap-free polymer agglomerating agent contains oligomers; the molecular structure of the oligomers contains hydrophilic groups and lipophilic groups; the weight average molecular weight of the oligomers is 300-5000; the hydrophilic groups include amide groups and / or carboxyl groups.

2. The soap-free polymer agglomerating agent according to claim 1, characterized in that The lipophilic group includes an ester group; Preferably, the mass percentage of oligomers in the soap-free polymer agglomerator is ≤10%, more preferably 3.5-7%.

3. The soap-free polymer agglomerating agent according to claim 1 or 2, characterized in that The oligomer comprises at least one compound having a structure shown in Formula I and / or at least one polymer having a structure shown in Formula II: In formula I, R1 and R2 are each independently selected from H or C1-C10 straight chain or branched alkyl; R3 is selected from H, C1-C10 straight chain or branched alkyl or -(CH2)n 11 -COOH; R4 is selected from -(CH2)n 21 -CONR N1 R N2 、-N(R N3 ) any one of CO-R7 or -COOH; n1, n2, n 11 、n 21 are each independently selected from an integer greater than or equal to 0; R N1 , R N2 , R N3 , R7 are each independently selected from H or C1-C10 straight or branched alkyl; In formula II, R1 and R2 are each independently selected from H or C1-C10 straight chain or branched alkyl; R3 and R5 are each independently selected from H, C1-C10 straight chain or branched alkyl or -(CH2)n 12 -COOH; R4, R6 are each independently selected from -(CH2)n 22 -CONR N1 R N2 、-N(R N3 ) any one of CO-R7 or -COOH; and one of R4 and R6 is selected from -COOH; n1, n2, n3, n4 12 、n 22 are each independently selected from an integer greater than or equal to 0; R N1 , R N2 , R N3 , R7 are each independently selected from H or C1~C10 straight or branched chain alkyl.

4. The soap-free polymer agglomerating agent according to any one of claims 1 to 3, characterized in that The raw materials for preparing the soap-free polymer agglomerating agent include monomers and initiators; the monomers include hydrophilic monomers and lipophilic monomers; the mass of the initiator is 0.1-5% of the total mass of the monomers; Preferably, the molar ratio of the hydrophilic monomer to the lipophilic monomer is (0.05-0.8):1, and more preferably the molar ratio is (0.09-0.55):1; Preferably, the hydrophilic monomer comprises an amide monomer and / or a carboxyl group-containing monomer; Preferably, the amide monomer includes at least one of acrylamide, N-tert-butylacrylamide, erucamide, oleamide, and N-methyl-N-vinylacetamide; Preferably, the carboxyl group-containing monomer includes at least one of (meth)acrylic acid, itaconic acid, and fumaric acid; Preferably, the oleophilic monomer comprises alkyl (meth)acrylate and / or vinyl acetate; Preferably, the alkyl (meth)acrylate includes at least one of methyl methacrylate, n-butyl acrylate, butyl methacrylate, isooctyl acrylate, ethyl acrylate and tert-butyl acrylate.

5. The soap-free polymer agglomerating agent according to claim 4, characterized in that The initiator includes at least one of an inorganic peroxide initiator, an azo initiator, and an organic peroxide initiator; Preferably, the preparation raw materials also include a cross-linking agent; Preferably, the mass of the cross-linking agent is 3 to 17% of the total mass of the monomers, more preferably 3.5 to 12%; Preferably, the crosslinking agent includes at least one of 1,4-butanediol diacrylate, ethylene glycol dimethacrylate, p-toluenesulfonic acid, p-toluenesulfonyl chloride, and divinylbenzene; Preferably, the gel content of the soap-free polymer agglomerating agent is 34 to 92%, more preferably the gel content is 50 to 89%; Preferably, the raw materials for preparation further include a chain transfer agent, and the mass of the chain transfer agent is 0.1 to 3% of the total mass of the monomers; Preferably, the number average molecular weight of the soap-free polymer agglomerating agent is 10,000 to 55,000; Preferably, the soap-free polymer agglomerator has a core-shell structure.

6. A method for preparing a soap-free polymer agglomerating agent according to any one of claims 1 to 5, characterized in that: The preparation method comprises the following steps: The hydrophilic monomer, the lipophilic monomer, the initiator and the solvent are mixed and reacted to obtain the soap-free polymer agglomerating agent.

7. The preparation method according to claim 6, characterized in that: The mixed raw materials also include a cross-linking agent and / or a chain transfer agent; Preferably, the reaction comprises the following steps: S1: mixing a hydrophilic monomer accounting for 1 to 95% of the total mass of the hydrophilic monomer and a lipophilic monomer accounting for 5 to 30% of the total mass of the lipophilic monomer to obtain a mixed monomer; then mixing the mixed monomer, an initiator in a formula amount of 9 to 99.8%, a solvent and an optional chain transfer agent, and reacting to obtain a product A; S2: mixing the product A obtained in step S1 with 6-55% of the total mass of the lipophilic monomers and the remaining initiator, and reacting to obtain product B; S3: mixing the remaining hydrophilic monomer and the remaining lipophilic monomer to obtain a mixed monomer; then mixing the product B obtained in step S2 with the mixed monomer and an optional cross-linking agent, reacting to obtain the soap-free polymer agglomerating agent; The molar ratio of the hydrophilic monomer to the lipophilic monomer in the mixed monomer in step S1 is (0.03-2.7):1; The molar ratio of the hydrophilic monomer to the lipophilic monomer in the mixed monomer in step S3 is (0.03-1.82):

1.

8. The preparation method according to claim 7, characterized in that: The molar ratio of the hydrophilic monomer to the lipophilic monomer in the mixed monomer of step S1 is (0.2-1.2):1; Preferably, the reaction in step S1 is carried out in the presence of a protective atmosphere; Preferably, the reaction temperature in step S1 is 50-83°C, the rotation speed is 120-200 rpm, and the reaction time is 10-120 min; Preferably, the reaction temperature in step S2 is 55-85°C and the reaction time is 30-85min; Preferably, the molar ratio of the hydrophilic monomer to the lipophilic monomer in the mixed monomer in step S3 is (0.12-0.9):1; Preferably, the method of adding the mixed monomer in step S3 comprises dropwise addition, and the time of the dropwise addition is 40 to 200 minutes; Preferably, the reaction temperature in step S3 is 70-87° C. and the reaction time is 25-180 min.

9. An agglomerated polybutadiene, characterized in that: The agglomerated polybutadiene comprises base polybutadiene and an agglomerating agent; the agglomerating agent comprises the soap-free polymer agglomerating agent according to any one of claims 1 to 5; Preferably, the dry basis mass of the soap-free polymer agglomerating agent is 0.1 to 20 parts based on 100 parts of the base polybutadiene; Preferably, the ratio of the D50 particle size of the agglomerated polybutadiene to the D50 particle size of the base polybutadiene is ≥2, more preferably ≥3.

10. An ABS resin, characterized in that: The raw materials for preparing the ABS resin include the agglomerated polybutadiene according to claim 9; Preferably, the yellowness index of the ABS resin is ≤18; Preferably, the ABS resin has an Izod notched impact strength of ≥10 KJ·m -2 .

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