Soap-free polymeric agglomerant, preparation method therefor, and use thereof

Abstract

Disclosed are a soap-free polymeric agglomerant, a preparation method therefor, and a use thereof. The soap-free polymeric agglomerant comprises an oligomer, the molecular structure of the oligomer comprises a hydrophilic group and a lipophilic group, the weight-average molecular weight of the oligomer is 300-5000, and the hydrophilic group includes an amido group and / or a carboxyl group. In the present application, the soap-free polymeric agglomerant has a good agglomeration effect and can achieve agglomeration to obtain a large-particle-size polybutadiene-based latex. Moreover, the polymeric agglomerant contains no emulsifier, thereby avoiding the introduction of excessive emulsifier during the preparation of an ABS graft polymer, thus facilitating improving the coagulation efficiency of an ABS latex and improving the impact resistance of an ABS resin, and reducing the yellow index of the ABS resin.

Description

A soap-free polymer agglomerant, its preparation method and application Technical Field

[0001] This application relates to the field of polymer materials technology, such as a soap-free polymer agglomerant, its preparation method, and its application. Background Technology

[0002] ABS resin is one of the world's five major synthetic resins, a graft copolymer of polybutadiene latex (PBL latex) with styrene and acrylonitrile. ABS resin is a polymer material between general-purpose plastics and engineering plastics, possessing excellent impact resistance, heat resistance, and chemical resistance. Furthermore, the impact resistance of ABS resin increases with the increase in the particle size of the rubber core. Therefore, when preparing ABS resin from PBL latex, a one-step or two-step method is used to pre-prepare large-particle-size PBL latex, thereby improving the performance of the ABS resin.

[0003] Before the 1980s, a one-step process for preparing large-particle-size PBL latex required over 40 hours to reach 300 nm. While technological advancements have reduced the reaction time to around 20 hours, this remains a constraint on production capacity. A two-step process for preparing large-particle-size PBL latex involves scaling up small-particle-size PBL latex using agglomeration methods. Related agglomeration methods include physical agglomeration (such as pressure agglomeration, freeze agglomeration, and mechanical stirring agglomeration); chemical agglomeration (such as acid agglomeration and organic solvent agglomeration); and polymer agglomeration (such as nonionic latex and unsaturated carboxylic acid copolymer latex). Among these, polymer agglomeration is the most widely used and best-performing method.

[0004] For example, patent CN113754797A provides a polymeric agglomerating agent latex, which uses ethyl acrylate and methyl methacrylate as raw materials and obtains the polymeric agglomerating agent through emulsion polymerization in a certain ratio; the polymeric agglomerating agent can expand the latex particle size from 80~110nm to 280~330nm in half an hour. However, the polymeric agglomerating agent latex contains emulsifiers, which are prone to causing secondary nucleation during subsequent graft polymerization, generating small-diameter latex particles, which not only affects the coagulation process but also affects the performance of the final product, such as yellowness, mechanical properties, gloss, and aesthetics.

[0005] Patent CN113651903A discloses a method for preparing large-particle-size polybutadiene latex based on polymer agglomeration technology. It uses vinyl sulfate or vinyl sulfonate as reactive emulsifiers and ionic comonomers instead of traditional acrylic acid comonomers, avoiding the use of any adsorbent emulsifiers. While the agglomerator obtained by this method can improve the influence of emulsifiers on material properties to some extent, it is still an emulsifier-type monomer, and the improvement effect needs further enhancement.

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

[0007] The following is an overview of the subject matter described in detail herein. This overview is not intended to limit the scope of the claims.

[0008] To address the shortcomings of related technologies, the purpose of this application is to provide a soap-free polymeric agglomerating agent, its preparation method, and its application. The soap-free polymeric agglomerating agent exhibits good agglomeration effect, enabling the agglomeration of large-particle-size polybutadiene latex, while the resulting agglomerated polybutadiene latex possesses good stability. Furthermore, the polymeric agglomerating agent does not contain emulsifiers, avoiding the secondary nucleation of the emulsion into SAN polymers and small-particle-size latex particles during the preparation of ABS graft polymers due to the introduction of excessive emulsifiers. This is beneficial for improving the coagulation efficiency of ABS latex and enhancing the performance of ABS resin.

[0009] To achieve this objective, the following technical solution is adopted in this application:

[0010] This application provides a soap-free polymer agglomerator, wherein the soap-free polymer agglomerator 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.

[0011] In this application, the oligomer contains hydrophilic and lipophilic groups in its molecular structure, exhibiting a molecular structure similar to that of an emulsifier. This allows it to function as an emulsifier, ensuring the stable synthesis of soap-free polymer agglomerates and providing excellent long-term stability. When used to agglomerate polybutadiene latex, it exhibits good agglomeration effect, resulting in large-particle-size and highly stable polybutadiene latex. Furthermore, since no external emulsifier is added, when using the agglomerated polybutadiene latex as a raw material to prepare ABS resin, excessive emulsifier will not affect the performance of the ABS resin, resulting in ABS resin with better impact resistance, lower yellow index, and a more aesthetically pleasing appearance.

[0012] In this application, the soap-free polymer agglomerator refers to a polymer agglomerator whose raw materials do not include emulsifiers.

[0013] In this application, the weight-average molecular weight of the oligomer is 300 to 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 any of the above values; it can be selected as 400 to 3500, or 405 to 1950.

[0014] In this application, the weight-average molecular weight of the oligomer and the number-average molecular weight of the soap-free polymer agglomerator were obtained by gel permeation chromatography. Specifically, tetrahydrofuran was used as the mobile phase, the sample concentration was 4 mg / mL, and the injection volume was 10 μL. The specific testing standard referred to GB / T 27843-2011 "Determination of Low Molecular Weight Components in Chemical Polymers by Gel Permeation Chromatography (GPC)". The weight-average molecular weight of the oligomer within the above range can provide good self-emulsification effect, and thus, when used to agglomerate polybutadiene latex, it has a good agglomeration effect and can obtain polybutadiene latex with large particle size. Moreover, the ABS resin prepared from agglomerated polybutadiene latex has better impact resistance, lower yellow index, and is more aesthetically pleasing. If the weight-average molecular weight is too high or too low, the self-emulsification effect will be poor or even lost, affecting the performance of the soap-free polymer agglomerator, and thus affecting the impact resistance and yellowing resistance of the final ABS resin.

[0015] Optionally, the lipophilic group includes an ester group.

[0016] Optionally, the mass percentage of oligomers in the soap-free polymer agglomerator is ≤10%, for example, it can be 0.1%, 0.2%, 0.5%, 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9%, 10% or any of the above values; it can be 3.5~7%.

[0017] In this application, 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:

[0018] ; .

[0019] In Formula I, R1 and R2 are each independently selected from H or C1~C10 straight-chain or branched alkyl groups; R3 is selected from H, C1~C10 straight-chain or branched alkyl groups or -(CH2)n. 11At least one of -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 Each is independently selected from integers greater than or equal to 0; R N1 R N2 R N3 R7 are each independently selected from H or C1~C10 straight-chain or branched alkyl groups.

[0020] In Formula II, R1 and R2 are each independently selected from H or C1-C10 straight-chain or branched alkyl groups; R3 and R5 are each independently selected from H, C1-C10 straight-chain or branched alkyl groups or -(CH2)n 12 At least one of -COOH; R4 and 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, n 12 n 22 Each is independently selected from integers greater than or equal to 0; R N1 R N2 R N3 R7 are each independently selected from H or C1~C10 straight-chain or branched alkyl groups.

[0021] In this application, the oligomer is an oligomer formed during the preparation of soap-free polymer agglomerates. By adjusting the amount and type of monomers and the preparation process (including the order of addition of monomers, the addition ratio, and the reaction temperature and time in the preparation process), the molecular structure, weight-average molecular weight, and mass percentage of the oligomer in the soap-free polymer agglomerate can be adjusted.

[0022] In this application, the raw materials for preparing the soap-free polymer agglomerator 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, optionally 0.2~3%, optionally 0.5~2.5%.

[0023] In this application, the molar ratio of the hydrophilic monomer to the lipophilic monomer is (0.05~0.8):1, where the specific values ​​of (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, etc. The values ​​are 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 any range of the above values; the molar ratio of the hydrophilic monomer to the ester monomer may be (0.09~0.55):1.

[0024] Optionally, the hydrophilic monomer includes amide monomers and / or carboxyl-containing monomers.

[0025] Optionally, the amide monomer includes at least one of acrylamide, N-tert-butylacrylamide, erucamide, oleamide, and N-methyl-N-vinylacetamide.

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

[0027] Optionally, the lipophilic monomer includes alkyl (meth)acrylates and / or vinyl acetate.

[0028] Optionally, the alkyl methacrylate includes at least one of methyl methacrylate, n-butyl acrylate, butyl methacrylate, isooctyl acrylate, ethyl acrylate, and tert-butyl acrylate.

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

[0030] In this application, the inorganic peroxide initiator includes at least one of potassium persulfate, ammonium persulfate, hydrogen peroxide, and sodium persulfate; the azo initiator includes at least one of azobisisobutylamidine hydrochloride, azobisisobutylimidazoline hydrochloride, azobiscyanopentanoic acid, azobisisopropylimidazoline, azobisisobutyronitrile, azobisisoheptanenitrile, and dimethyl azobisisobutyrate; and the organic peroxide initiator includes cumene hydroperoxide and / or benzoyl peroxide.

[0031] Optionally, the raw materials used in the preparation may also include a crosslinking agent.

[0032] Optionally, 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 any range of the above values; optionally, it can be 3.5-12%.

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

[0034] Optionally, the gel content of the soap-free polymer agglomerator 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 any range of the above values; optionally, the gel content is 50-89%.

[0035] Optionally, the raw materials for preparation further include a chain transfer agent, wherein the mass of the chain transfer agent is 0.1-3% of the total mass of the monomers, optionally 0.2-2.5%, or optionally 0.5-1.5%.

[0036] In this application, the chain transfer agent includes at least one of dodecyl mercaptoacetic acid, mercaptopropionic acid, sodium bisulfite, mercaptoethanol, mercaptopropanol, formic acid, or sodium hypophosphite.

[0037] Optionally, the number average molecular weight of the soap-free polymer agglomerator is 10,000 to 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 any of the above values.

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

[0039] In this application, the core-shell structure of the soap-free polymer agglutinator is a polymer core formed by ester monomers, and the shell is a polymer outer shell formed by hydrophilic monomers.

[0040] In this application, the solid content of the soap-free polymer agglomerator is 28-50%.

[0041] Secondly, this application provides a method for preparing the soap-free polymer agglomerator described in the first aspect, the preparation method comprising the following steps:

[0042] The hydrophilic monomer, lipophilic monomer, initiator and solvent are mixed and reacted to obtain the soap-free polymer agglomerator.

[0043] In this application, the preparation method can form oligomers during the reaction process. The molecular structure of the oligomers contains hydrophilic and lipophilic groups, thereby giving the oligomers self-emulsifying properties. No emulsifier needs to be added; emulsion polymerization can be carried out by utilizing the surface activity of the oligomers, ensuring the polymerization reaction proceeds. At the same time, the resulting agglomerating latex has good stability. It is used to agglomerate polybutadiene latex and use the agglomerated polybutadiene latex as a raw material to prepare ABS resin, which can avoid the problem of poor impact resistance and yellowing resistance of ABS resin caused by the introduction of too much external emulsifier.

[0044] In this application, the solvent includes water; the mass of the solvent can be 25 to 200 parts by weight, for example, 25 parts, 50 parts, 75 parts, 100 parts, 125 parts, 150 parts, 175 parts, 195 parts or any range between the above values; the mass of the solvent is sufficient to make the solid content of the soap-free polymer agglomerator 28 to 50%.

[0045] Optionally, the mixed raw materials may further include crosslinking agents and / or chain transfer agents.

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

[0047] S1: A hydrophilic monomer comprising 1-95% (e.g., 1%, 5%, 9%, 10%, 20%, 30%, 40%, 50%, 60%, 70%, 80%, 90%, 95% or any range thereof) of the total mass of the hydrophilic monomers is mixed with a lipophilic monomer comprising 5-30% (e.g., 5%, 9%, 10%, 15%, 20%, 25%, 30% or any range thereof) of the total mass of the lipophilic monomers to obtain a mixed monomer; then the mixed monomers, an initiator comprising 9-99.8% (e.g., 9%, 10%, 20%, 30%, 40%, 50%, 60%, 70%, 80%, 90%, 95%, 99% or any range thereof), a solvent, and an optional chain transfer agent are mixed and reacted to obtain product A;

[0048] S2: Mix product A obtained in step S1 with 6-55% of the total mass of lipophilic monomers (for example, it can be 6%, 8%, 10%, 15%, 20%, 25%, 30%, 35%, 40%, 45%, 50%, 54% or any range between the above values) and the remaining initiator, and react to obtain product B.

[0049] S3: Mix the remaining hydrophilic monomer and the remaining lipophilic monomer 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 agglomerator.

[0050] In this application, the types of monomers added in steps S1, S2, and S3 are different. Hydrophilic and lipophilic monomers are added in S1 and S3, while only lipophilic monomers are added in S2. The added mass is calculated as 100% of the total mass of each monomer. The reason is as follows: In the early stage of the reaction, i.e., stage S1, surface-active oligomers are needed to provide emulsion polymerization stability; in the middle stage of the reaction, i.e., stage S2, the particle size growth period of the polymer agglomerator emulsion is underway, and hydrophobic ester monomers can diffuse into the micelles and continuously polymerize to increase the particle size; in the later stage of the reaction, i.e., stage S3, as the particle size of the polymer agglomerator latex increases, the original oligomer content is not enough to maintain emulsion stability, and surface-active oligomers need to be added to maintain emulsion stability.

[0051] Optionally, the molar ratio of hydrophilic monomer to ester monomer in the mixed monomers described in step S1 is (0.03~2.7):1, where the specific values ​​of (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. 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 any range of the above values; the optional molar ratio is (0.2~1.2):1.

[0052] In this application, the solvent in step S1 includes water; the mass of the solvent is 25 to 200 parts by weight, for example, 25 parts, 50 parts, 75 parts, 100 parts, 125 parts, 150 parts, 175 parts, 195 parts or any range between the above values.

[0053] Optionally, the reaction described in step S1 is carried out in the presence of a protective atmosphere.

[0054] In this application, the protective atmosphere includes, but is not limited to, nitrogen.

[0055] Optionally, the reaction temperature in step S1 is 50~83℃, for example, it can be 50℃, 52℃, 55℃, 58℃, 60℃, 62℃, 65℃, 68℃, 70℃, 72℃, 75℃, 78℃, 80℃, 82℃, 83℃ or any range of the above values; the rotation speed is 120~200 rpm, for example, it can be 120 rpm, 140 rpm, 160 rpm, 180 rpm, 200 rpm or any range of the above values; the time is 10~120 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 any range of the above values.

[0056] Optionally, the reaction temperature in step S2 is 55~85℃, for example, it can be 55℃, 56℃, 58℃, 60℃, 62℃, 64℃, 66℃, 68℃, 70℃, 72℃, 74℃, 76℃, 78℃, 80℃, 82℃, 84℃, 85℃ or any range between the above values; the time is 30~85 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 any range between the above values.

[0057] Optionally, in step S3, the molar ratio of hydrophilic monomer to lipophilic monomer in the mixed monomers is (0.03~1.82):1, where the specific values ​​in (0.03~1.82) 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, or 0.45. The values ​​can be 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 any range of the above values; the molar ratio can be (0.12~0.9):1.

[0058] Optionally, the method for adding the mixed monomers in step S3 includes dropwise addition, wherein the dropwise addition time is 40 to 200 minutes, for example, 40 minutes, 45 minutes, 50 minutes, 55 minutes, 60 minutes, 65 minutes, 70 minutes, 75 minutes, 80 minutes, 85 minutes, 90 minutes, 95 minutes, 100 minutes, 105 minutes, 110 minutes, 115 minutes, 120 minutes, 125 minutes, 130 minutes, 135 minutes, 140 minutes, 145 minutes, 150 minutes, 155 minutes, 160 minutes, 165 minutes, 170 minutes, 175 minutes, 180 minutes, 185 minutes, 190 minutes, 195 minutes, 200 minutes, or any range between the above values.

[0059] Optionally, the reaction temperature in step S3 is 70~87℃, for example, it can be 70℃, 72℃, 74℃, 76℃, 78℃, 80℃, 82℃, 84℃, 85℃, 86℃ or any range between the above values; the time is 25~180min, 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 any range between the above values.

[0060] As an optional technical solution in this application, the preparation method includes the following steps:

[0061] S1: Mix 1-95% of the total mass of hydrophilic monomers with 5-30% of the total mass of lipophilic monomers to obtain a mixed monomer; then mix the mixed monomers, 9-99.8% of the formulated amount of initiator, 25-200 parts of solvent, and optional chain transfer agent to obtain a mixed solution with a mass concentration of 2-50%; then react under nitrogen protection at a high shear speed of 120-200 rpm and a temperature of 50-83℃ for 10-120 min to obtain product A;

[0062] S2: Add 6-55% of the total mass of the lipophilic monomer and the remaining initiator to product A obtained in step S1, heat to 55-85℃, and react for 30-85 min to obtain product B;

[0063] S3: Mix the remaining hydrophilic monomer and the remaining lipophilic monomer to obtain a mixed monomer; then add the mixed monomer and an optional crosslinking agent dropwise to product B obtained in step S2, controlling the monomer dropwise addition time to be 40~200 min, raising the temperature to 70~87℃, and reacting for 25~180 min to obtain the soap-free polymer agglomerator.

[0064] Thirdly, this application provides an agglomerated polybutadiene, which includes a base polybutadiene and an agglomerating agent; the agglomerating agent includes the soap-free polymeric agglomerating agent described in the first aspect.

[0065] Optionally, based on 100 parts of the dry basis of the base polybutadiene, the dry basis addition mass of the soap-free polymer agglomerator is 0.1 to 20 parts, for example, it can be 0.1 parts, 0.5 parts, 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 any range between the above values; it can be 1.5 to 10.5 parts.

[0066] Optionally, the ratio of the D50 particle size of the agglomerated polybutadiene to the D50 particle size of the base polybutadiene is ≥2, optionally ≥3, and optionally 3.2~8.

[0067] In this application, the D50 particle size of the basic polybutadiene is 50~150nm; the D50 particle size of the agglomerated polybutadiene is 200~800nm; optionally, the D50 particle size of the basic polybutadiene is 50~120nm; and the D50 particle size of the agglomerated polybutadiene is 250~800nm.

[0068] In this application, the agglomerated polybutadiene can be prepared by conventional methods. For example, the preparation method includes: mixing the base polybutadiene emulsion (D50 particle size of 100 nm) with the soap-free polymer agglomerating agent and solvent (including deionized water) according to the formula amount, and stirring for 100-150 min at 25℃~50℃ and 40~100 rpm to obtain the agglomerated polybutadiene.

[0069] In this application, the basic polybutadiene emulsion can be obtained commercially or prepared using conventional methods. For example, the preparation method includes: mixing 100 parts butadiene, 0.5-6 parts initiator, 0.1-1 part electrolyte, 1-6 parts emulsifier, 0.1-0.5 parts chain transfer agent, and 150-250 parts solvent evenly, then heating to 60-80°C to begin the polymerization reaction. During the reaction, samples are taken, and the reaction reaches its endpoint when the monomer conversion rate is ≥90% by drying method, thus obtaining the basic polybutadiene emulsion; the initiator, electrolyte, emulsifier, and... The chain transfer agent can be any conventional additive in the art; such as initiators including but not limited to potassium persulfate, ammonium persulfate, azobisisobutyronitrile, azobisisoheptanenitrile, dimethyl azobisisobutyrate, cumene hydroperoxide, or benzoyl peroxide; a redox initiation system can also be used, with the addition of a reducing agent, such as ferrous sulfate, ferric chloride, or sodium formaldehyde sulfoxylate; the electrolyte includes but is not limited to potassium carbonate; the emulsifier includes but is not limited to potassium rosin soap, potassium oleate, or alkylphenol polyoxyethylene ether; the chain transfer agent includes but is not limited to dodecyl mercaptan, mercaptoacetic acid, mercaptopropionic acid, sodium bisulfite, or formic acid.

[0070] Fourthly, this application provides an ABS resin, wherein the raw materials for preparing the ABS resin include the agglomerated polybutadiene described in the second aspect.

[0071] In this application, the raw materials for preparing 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 amount of the comonomer is 20-150 parts, for example, 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 any range between the above values; the amount of the initiator is 0.5-25 parts, for example, 0.5 parts. The amount of emulsifier is 4.5 to 15.5 parts, for example, 4.5, 5, 6, 8, 10, 12, 14, 16, 18, 20, 22, 24, 25 parts or any of the above values; the amount of chain transfer agent is 1 to 6 parts, for example, 1, 2, 3, 4, 5, 6 parts or any of the above values.

[0072] In this application, the comonomer includes aromatic vinyl monomers and alkenyl nitrile monomers; the mass percentage of aromatic vinyl monomers in the comonomer is 60-90%, for example, it can be 60%, 65%, 70%, 75%, 80%, 85%, 90% or any range between the above values.

[0073] In this application, the raw materials for preparing the ABS resin include, but are not limited to, styrene as an aromatic vinyl monomer and, but are not limited to, acrylonitrile or methacrylonitrile as alkenyl nitrile monomers. Furthermore, there are no particular restrictions on the types of initiators, emulsifiers, and chain transfer agents; conventional additives in the art can be used. Initiators include, but are not limited to, potassium persulfate, ammonium persulfate, azobisisobutyronitrile, azobisisoheptanenitrile, dimethyl azobisisobutyrate, cumene hydroperoxide, or benzoyl peroxide. A redox initiation system can also be used, with the addition of reducing agents such as ferrous sulfate, ferric chloride, or sodium formaldehyde sulfoxylate. Emulsifiers include, but are not limited to, potassium rosinate, potassium oleate, or alkylphenol polyoxyethylene ether. Chain transfer agents include, but are not limited to, dodecyl mercaptoacetic acid, mercaptopropionic acid, sodium bisulfite, or formic acid.

[0074] In this application, the ABS resin can be prepared using conventional methods. For example, the preparation method includes: mixing agglomerated polybutadiene with comonomers, initiators, emulsifiers, chain transfer agents, and solvents, and reacting at 40-80°C for 2-8 hours to obtain ABS grafted latex; then mixing the grafted latex with coagulants and solvents, coagulating at 70-100°C for 1-3 hours, and then coagulating at 80-110°C for 0.5-2.5 hours, washing, and drying to obtain the ABS resin.

[0075] In this application, the mass of the ABS grafted latex is 100 parts, and the amount of the coagulant is 5 to 15 parts, for example, 5 parts, 6 parts, 8 parts, 10 parts, 12 parts, 14 parts, 15 parts, or any range between the above values; the mass of the solvent is 300 to 700 parts, for example, 300 parts, 350 parts, 400 parts, 450 parts, 500 parts, 550 parts, 600 parts, 650 parts, 700 parts, or any range between the above values; the solvent includes water.

[0076] Optionally, the yellow index of the ABS resin is ≤18, optionally ≤16.5, or optionally ≤15.

[0077] Optionally, the notched impact strength of the ABS resin is ≥10 kJ / m. 2 Optional cantilever beam notched impact strength ≥15 kJ / m 2 Optional cantilever beam notched impact strength ≥20 kJ / m 2 .

[0078] The numerical range described in this application includes not only the point values ​​listed above, but also any point values ​​between the above numerical ranges that are not listed. Due to space limitations and for the sake of brevity, this application will not exhaustively list the specific point values ​​included in the range.

[0079] Compared with related technologies, the beneficial effects of this application are as follows:

[0080] The soap-free polymer agglomerator provided in this application does not contain emulsifiers and contains oligomers with hydrophilic and lipophilic groups, which can provide self-emulsifying properties and ensure the stability of the agglomerator. When used to agglomerate polybutadiene latex, it not only has a good agglomeration effect and can obtain polybutadiene latex with large particle size, but also, when ABS resin is prepared from agglomerated polybutadiene latex as raw material, the obtained ABS resin has better impact resistance, lower yellow index, and is more aesthetically pleasing.

[0081] After reading and understanding the detailed description, other aspects can be understood. Detailed Implementation

[0082] The technical solution of this application will be further illustrated below through specific embodiments. Those skilled in the art should understand that the embodiments described are merely illustrative of this application and should not be construed as specific limitations thereof.

[0083] All materials used in the embodiments and comparative examples of this application can be obtained commercially available materials or prepared using conventional methods. Unless otherwise specified, the materials used in this application are commercially available.

[0084] In this application, the method for testing the gel content includes: referring to the industry standard SH / T 1050-2014, "Determination of Gel Content in Synthetic Raw Rubber". The specific method is as follows: The obtained soap-free polymer agglomerator emulsion is spread evenly on a smooth plate to obtain a film with a thickness of 0.2 mm to 0.7 mm. After natural air drying until no flow occurs, it is placed in a forced-air drying oven and dried at 80°C for 2 hours. Then, the film is removed from the plate and placed in a desiccator for 5 to 10 minutes to allow it to return to room temperature. 0.25 g ± 0.0050 g of the film is taken, recorded as m, accurate to 0.0001 g, and placed into a pre-weighed filter (made of 120-mesh stainless steel sieve). The filter is then placed in a 200 mL beaker. Approximately 50 mL of toluene is added to the beaker, ensuring the sample is completely immersed in toluene. The beaker is covered with plastic wrap and aluminum foil and placed in a fume hood in the dark, at 23 ± 5°C for 16 to 24 hours to dissolve. After complete dissolution, remove the filter from the beaker with tweezers. Use a pipette to draw an appropriate amount of toluene and rinse the filter and the gel within it to remove any residual solvent. Rinse four times. Then, place the filter on an enamel dish lined with clean filter paper or wire mesh and ventilate it in a fume hood for 2 hours. After that, dry the filter in an oven at 100℃±2℃ for 1 hour. Remove it and place it in a desiccator for 5-10 minutes, then weigh and record the result. Place it back in the oven to dry for another 30 minutes, remove it, cool and dry it, and weigh and record the result again. Repeat this process until the difference between two weighings is ≤0.3 mg.

[0085] The formula for calculating gel content is:

[0086]

[0087] In the formula:

[0088] m2—Mass of the polymer insoluble in toluene and the sieve (after drying), in g;

[0089] m1—mass of the sieve, in grams;

[0090] m — Sample mass, g.

[0091] The D50 particle size was obtained by laser nanoparticle size analyzer. Specifically, deionized water was used as the solvent to dilute the sample to approximately 0.01% by mass, and the sample was added to 1 / 3 of the sample cell before testing. The number-average molecular weight, weight-average molecular weight, and mass percentage of oligomers were obtained by gel permeation chromatography. The specific method is as follows:

[0092] The mobile phase was tetrahydrofuran, the test temperature was 40℃, the flow rate was 0.5 mL / min, the standard sample was polystyrene, and the chromatographic column model was pl-mixed-c. Approximately 1 g of soap-free polymer agglomerate was placed in a weighing bottle and dried at 120℃ for 30 min. The dried film was then dissolved in tetrahydrofuran to a concentration of 4 mg / mL and filtered through a micropore into a sample vial. The number-average molecular weight and weight-average molecular weight of the soap-free polymer agglomerate and its oligomers could then be measured. The peak area of ​​the obtained GPC test curve was integrated; the ratio of the area of ​​the low molecular weight peak to the area of ​​the full spectrum peaks represented the mass percentage of the oligomer.

[0093] Example 1

[0094] This embodiment provides a soap-free polymer agglomerator. By weight, the raw materials for preparing the soap-free polymer agglomerator include monomers, a crosslinking agent (divinylbenzene) accounting for 5.5% of the total monomer mass, an initiator (azobisisobutyronitrile) accounting for 0.44% of the total monomer mass, and a chain transfer agent (mercaptopropionic acid) accounting for 0.55% of the total monomer mass. The monomers include a hydrophilic monomer (fumaric acid) and a lipophilic monomer (ethyl acrylate) in a molar ratio of 0.1:1.

[0095] This embodiment provides a method for preparing the soap-free polymer agglomerator, specifically including the following steps:

[0096] S1: Fumaric acid, accounting for 40.8% of the total mass of hydrophilic monomers, and ethyl acrylate, accounting for 18.5% of the total mass of lipophilic monomers, are mixed to obtain a mixed monomer with a molar ratio of fumaric acid to ethyl acrylate of 0.23:1. Then, the mixed monomers, 50% of the formulation amount of initiator, chain transfer agent, and water are mixed in a reaction flask. After purging with nitrogen three times, stirring is started and the temperature is rapidly raised to 60°C. The reaction is carried out under the condition of heat preservation for 120 min to obtain product A.

[0097] S2: Add 34.6% of the total mass of the lipophilic monomers and the remaining initiator to product A obtained in step S1, heat to 75°C, and react for 60 min to obtain product B;

[0098] S3: Add crosslinking agent to product B obtained in step S2, and add the remaining monomer, i.e., a mixture of fumaric acid and ethyl acrylate in a molar ratio of 0.13:1, controlling the dropping time to 180 min, raising the temperature to 82°C, and reacting for 30 min to obtain the soap-free polymer agglomerator with a solid content of 45±1%.

[0099] Examples 2-18 provide a soap-free polymer agglomerator, which differs from Example 1 only in the types and amounts of raw materials, the percentage of hydrophilic monomers and lipophilic monomers added in steps S1 and S3 of the preparation method, the percentage of lipophilic monomers added in step S2, or the molar ratio of hydrophilic monomers to lipophilic monomers in the mixed monomers in steps S1 and S3; specific parameters are shown in Tables 1-3; everything else is the same as Example 1.

[0100] The number-average molecular weight, weight-average molecular weight of the oligomers, and mass percentage of the oligomers provided in Examples 1-18 are shown in Tables 1-3; wherein, the values ​​corresponding to the hydrophilic monomer and the lipophilic monomer represent their molar ratio; 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; " / " indicates that the raw material is not present.

[0101] In the preparation method of Example 18, the order of monomer addition is different. Specifically, S1 is the addition of ethyl acrylate, which accounts for 34.6% of the total mass of the lipophilic monomers, and S2 is the addition of a mixed monomer. The mixed monomer is a mixture of fumaric acid, which accounts for 40.8% of the total mass of the hydrophilic monomers, and ethyl acrylate, which accounts 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, dosages, and step parameters are the same as in Example 1.

[0102]

[0103]

[0104]

[0105] Comparative Example 1

[0106] This comparative example provides a polymer agglomerant, which differs from Example 1 only in that the raw materials for preparation also include potassium oleate emulsifier (5.7% by mass of the total mass of hydrophilic and lipophilic monomers). In the preparation method, the raw materials mixed in step S1 also include potassium oleate. Other raw materials, amounts, and step parameters are the same as in Example 1.

[0107] Comparative Example 2

[0108] This comparative example provides a soap-free polymeric agglomerant, which differs from Example 1 only in that the total mass of the monomer remains unchanged, and the monomer is dimethylaminoethyl methacrylate, so that the hydrophilic groups in the oligomer of the obtained soap-free polymeric 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 hours to obtain the soap-free polymeric agglomerant.

[0109] Application Example 1

[0110] An agglomerated polybutadiene, wherein the agglomerated polybutadiene is an agglomerated polybutadiene latex, comprising a base polybutadiene latex (D50 particle size of 100 nm) and an agglomerating agent; the agglomerating agent is the polymeric agglomerating agent provided in Examples 1-18 and Comparative Examples 1-2; the D50 particle size, agglomerating agent type and dosage (based on 100 parts of dry basis of the base polybutadiene latex) of the agglomerated polybutadiene latex are shown in Table 4.

[0111] The preparation method of the basic polybutadiene latex is as follows: 100 parts butadiene, 1.5 parts potassium persulfate, 1.5 parts cumene hydroperoxide, 0.5 parts potassium carbonate, 3 parts potassium rosin soap, 0.3 parts dodecyl mercaptan, and 200 parts deionized water are added to a reactor and mixed evenly. The temperature is raised to 68°C to start the polymerization reaction. During the reaction, samples are taken, and the monomer conversion rate is tested by drying method. When the monomer conversion rate reaches 90%, the reaction reaches the endpoint, and the basic polybutadiene latex is obtained.

[0112] The preparation method of the agglomerated polybutadiene includes: taking 100 parts by mass of basic polybutadiene latex (D50 particle size of 100 nm) on a dry basis, and a certain amount of soap-free polymer agglomerating agent (prepared in the example) (see Table 4 for the agglomerating agent parts), 50 parts of deionized water, adding them into a reaction vessel, starting the stirring, stirring at low speed (80 rpm) for 120 min and then stopping, to obtain the agglomerated polybutadiene.

[0113]

[0114] As shown in Table 4, the soap-free polymer agglomerating agent provided in this application has a good agglomeration effect, and can agglomerate basic polybutadiene latex with a D50 particle size of 100nm to obtain agglomerated polybutadiene with a D50 particle size of 200~800nm, which can be selected as 330~620nm; while the agglomerating agents provided in Comparative Examples 1 and 2 have poor agglomeration effects, and the D50 particle size of the agglomerated polybutadiene is smaller.

[0115] Application Example 2

[0116] An ABS resin, wherein the preparation method of the ABS resin includes:

[0117] (1) Add butadiene polymer emulsion to the reactor, and then add 0.015 parts of ferric sulfate and 3 parts of sodium formaldehyde sulfoxylate to 100 parts of dry butadiene polymer emulsion. Stir evenly, heat the reactor to 67°C, and add 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. Add continuously for 2 hours, and continue to react for 5 hours after heating is completed to obtain ABS grafted latex.

[0118] (2) Mix 100 parts of ABS grafted latex obtained in step (1) with 500 parts of deionized water and 10 parts of magnesium sulfate, turn on the stirrer and heat to 85°C, stir for 2 hours, then raise the temperature to 95°C and continue stirring for 1.5 hours. After washing the suspension with deionized water several times, dry it and obtain the ABS resin after constant weight, that is, obtain ABS powder.

[0119] In step (1), the butadiene polymer emulsions are polybutadiene latexes provided in Application Examples 1 to 24.

[0120] Performance testing

[0121] (1) Notched impact strength of cantilever beam: Tested in accordance with standard GB / T 1843-2008, "Determination of impact strength of plastic cantilever beam";

[0122] (2) Yellow index: Tested in accordance with standard GB / T 39822-2021, "Determination of Yellow Index and Variation Value of Plastics".

[0123] The specific test results are shown in Table 5.

[0124]

[0125] As shown in Table 5, the ABS resin prepared using polybutadiene latex agglomerated with the soap-free polymer agglomerator provided in this application as raw material has high impact strength and a low yellow index; the cantilever beam notched impact strength of the ABS resin is ≥10.8 kJ / m. 2 The yellow index is ≤18; it can even reach a cantilever beam notched impact strength ≥20.2 kJ / m. 2 Yellow index ≤ 15.

[0126] As can be seen from the comparative examples, the ABS resin obtained by the agglomerating agent that is not specific to this application has poor impact resistance, high yellow index, and poor color aesthetics.

Claims

1. A soap-free polymer agglomerator containing oligomers; the molecular structure of the oligomers contains hydrophilic 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 agglomerant according to claim 1, wherein, The lipophilic group includes an ester group; Optionally, the mass percentage of oligomers in the soap-free polymer agglomerator is ≤10%, and can be 3.5~7%.

3. The soap-free polymer agglomerant according to claim 1 or 2, wherein, 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: ； ； In Formula I, R1 and R2 are each independently selected from H or C1~C10 straight-chain or branched alkyl groups; R3 is selected from H, C1~C10 straight-chain or branched alkyl groups or -(CH2)n 11 At least one of -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 Each is independently selected from integers greater than or equal to 0; R N1 R N2 R N3 R7 are each independently selected from H or C1~C10 straight-chain or branched alkyl groups; In Formula II, R1 and R2 are each independently selected from H or C1-C10 straight-chain or branched alkyl groups; R3 and R5 are each independently selected from H, C1-C10 straight-chain or branched alkyl groups or -(CH2)n 12 At least one of -COOH; R4 and 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, n 12 n 22 Each is independently selected from integers greater than or equal to 0; R N1 R N2 R N3 R7 are each independently selected from H or C1~C10 straight-chain or branched alkyl groups.

4. The soap-free polymer agglomerant according to any one of claims 1 to 3, wherein, The raw materials for preparing the soap-free polymer agglomerator 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; Optionally, the molar ratio of the hydrophilic monomer to the lipophilic monomer is (0.05~0.8):1, and optionally the molar ratio is (0.09~0.55):

1.

5. The soap-free polymer agglomerant according to claim 4, wherein, The hydrophilic monomers include amide monomers and / or carboxyl-containing monomers; Optionally, the amide monomer includes at least one of acrylamide, N-tert-butylacrylamide, erucamide, oleamide, and N-methyl-N-vinylacetamide; Optionally, the carboxyl-containing monomer includes at least one of (meth)acrylic acid, itaconic acid, and fumaric acid; Optionally, the lipophilic monomer includes alkyl (meth)acrylates and / or vinyl acetate; Optionally, the alkyl methacrylate includes at least one of methyl methacrylate, n-butyl acrylate, butyl methacrylate, isooctyl acrylate, ethyl acrylate, and tert-butyl acrylate.

6. The soap-free polymer agglomerant according to claim 4 or 5, wherein, The initiator includes at least one of inorganic peroxide initiators, azo initiators, or organic peroxide initiators.

7. The soap-free polymer agglomerant according to any one of claims 4 to 6, wherein, The raw materials used in the preparation also include a crosslinking agent; Optionally, the crosslinking agent accounts for 3-17% of the total mass of the monomers, and is optionally 3.5-12%. Optionally, the crosslinking agent includes at least one of 1,4-butanediol diacrylate, ethylene glycol dimethacrylate, p-toluenesulfonic acid, p-toluenesulfonyl chloride, and divinylbenzene; Optionally, the raw materials for preparation may further include a chain transfer agent, wherein the mass of the chain transfer agent is 0.1-3% of the total mass of the monomers.

8. The soap-free polymer agglomerant according to any one of claims 1 to 7, wherein, The gel content of the soap-free polymer agglomerator is 34-92%, and optionally 50-89%. Optionally, the number average molecular weight of the soap-free polymer agglomerator is 10,000 to 55,000; Optionally, the soap-free polymer agglomerant has a core-shell structure.

9. A method for preparing a soap-free polymer agglomerant according to any one of claims 1 to 8, comprising the following steps: The hydrophilic monomer, lipophilic monomer, initiator and solvent are mixed and reacted to obtain the soap-free polymer agglomerator.

10. The preparation method according to claim 9, wherein, The mixed raw materials also include crosslinking agents and / or chain transfer agents; Optionally, the reaction includes the following steps: S1: Mix 1-95% of the total mass of hydrophilic monomers with 5-30% of the total mass of lipophilic monomers to obtain a mixed monomer; then mix the mixed monomers, 9-99.8% of the formulation amount of initiator, solvent and optional chain transfer agent, and react to obtain product A; S2: Mix product A obtained in step S1 with 6-55% of the total mass of the lipophilic monomer and the remaining initiator, and react to obtain product B; S3: Mix the remaining hydrophilic monomer and the remaining lipophilic monomer 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 agglomerator. In step S1, the molar ratio of hydrophilic monomer to lipophilic monomer in the mixed monomers is (0.03~2.7):1; In step S3, the molar ratio of hydrophilic monomer to lipophilic monomer in the mixed monomer is (0.03~1.82):

1.

11. The preparation method according to claim 10, wherein, In step S1, the molar ratio of hydrophilic monomer to lipophilic monomer in the mixed monomer is (0.2~1.2):1; Optionally, the reaction described in step S1 is carried out in the presence of a protective atmosphere; Optionally, the reaction temperature in step S1 is 50~83℃, the rotation speed is 120~200 rpm, and the time is 10~120 min; Optionally, the reaction in step S2 is carried out at a temperature of 55-85°C for 30-85 minutes.

12. The preparation method according to claim 10 or 11, wherein, In step S3, the molar ratio of hydrophilic monomer to lipophilic monomer in the mixed monomer is (0.12~0.9):1; Optionally, the method for adding the mixed monomers in step S3 includes dropwise addition, wherein the dropwise addition time is 40~200 min; Optionally, the reaction in step S3 is carried out at a temperature of 70-87°C for a time of 25-180 min.

13. An agglomerated polybutadiene, comprising a base polybutadiene and an agglomerating agent; said agglomerating agent comprising the soap-free polymeric agglomerating agent according to any one of claims 1 to 8; Optionally, based on 100 parts of the dry basis of the base polybutadiene, the dry basis of the soap-free polymer agglomerating agent is added in the amount of 0.1 to 20 parts. Optionally, the ratio of the D50 particle size of the agglomerated polybutadiene to the D50 particle size of the base polybutadiene is ≥2, and optionally the ratio is ≥3.

14. An ABS resin, wherein the raw materials for its preparation include the agglomerated polybutadiene as described in claim 13; Optionally, the yellowness index of the ABS resin is ≤18; Optionally, the notched impact strength of the ABS resin is ≥10 kJ / m. 2 .

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