Agglomerated particle, and preparation method therefor and use thereof

Abstract

Provided in the present application are an agglomerated particle, and a preparation method therefor and the use thereof. The agglomerated particle comprises a vinyl-based polymer and a coagulant, wherein the coagulant comprises a cationic polymer; a nitrogen-containing functional group is present in the molecular structure of the cationic polymer; and the addition amount of the cationic polymer is 0.2-27 parts on the basis of the addition amount of the vinyl-based polymer being 100 parts. The agglomerated particle has a long oxidation induction time, a low yellowness index and a good thermo-oxidative aging resistance, and can be used as an impact modifier to improve the resistance of a resin composite material to impacts and thermo-oxidative aging-induced yellowing; moreover, the obtained resin composite material has good antimicrobial and mildew-proof properties.

Description

A condensed particle, its preparation method and application Technical Field

[0001] This application belongs to the field of latex coagulation material technology, specifically relating to a coagulated particle, its preparation method, and its application. Background Technology

[0002] Aromatic vinyl graft copolymers, such as butadiene-styrene-acrylonitrile copolymer (ABS), butadiene-methyl methacrylate-styrene-acrylonitrile copolymer (MABS), butadiene-methyl methacrylate-styrene copolymer (MBS), and acrylonitrile-styrene-acrylate monomer copolymer (ASA), are widely used in various fields, such as electronics, automobiles, and daily necessities, due to their excellent physical and mechanical properties.

[0003] Aromatic vinyl graft copolymers can be prepared by various methods, such as bulk polymerization, suspension polymerization, solution polymerization, and emulsion polymerization. Compared to other methods, emulsion polymerization more easily yields latexes with high molecular weights, specific particle sizes, or grafted structures, and is a commonly used synthesis method. However, emulsion polymerization produces latex; to obtain a solid product, a coagulant needs to be added to separate the polymer from the latex, forming latex aggregates. These latex aggregates can serve as excellent toughening agents for preparing resin composites, improving their impact resistance.

[0004] Currently, acids or metal salts are commonly used as coagulants in the latex of aromatic vinyl graft copolymers. However, using acids or metal salts for coagulation results in residual coagulants, leading to poor heat oxidation resistance and a high yellowing index in the resulting coagulated particles, thus affecting the heat oxidation resistance and yellowing resistance of the resin composites. Furthermore, long-term use and accumulation of resin composites can cause significant bacterial growth, threatening food safety and human health. Existing technologies often improve the antibacterial and antifungal properties of resin composites by adding antibacterial agents. However, inorganic antibacterial agents, such as silver ion antibacterial agents and ZnO series antibacterial agents, can affect the heat oxidation resistance of resin composites, while polymeric antibacterial agents can affect the mechanical properties of resin composites.

[0005] Therefore, developing a coagulated particle that combines excellent impact resistance, heat and oxygen aging resistance, and antibacterial and antifungal properties is an urgent problem to be solved in this field. Summary of the Invention

[0006] 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.

[0007] To address the shortcomings of existing technologies, the purpose of this application is to provide agglomerated particles, their preparation method, and applications. The agglomerated particles have a long oxidation induction period, a low yellowing index, and excellent resistance to heat and oxygen aging. They can be used as impact modifiers to improve the impact resistance, heat oxidation resistance, and aging yellowing resistance of resin composites. Simultaneously, they impart excellent antibacterial and antifungal properties to the resin composites.

[0008] To achieve this objective, the following technical solution is adopted in this application:

[0009] In a first aspect, this application provides a coagulating particle, the coagulating particle comprising a vinyl polymer and a coagulant; the coagulant comprising a cationic polymer; the cationic polymer having nitrogen-containing functional groups in its molecular structure; and the cationic polymer being added in an amount of 0.2 to 27 parts, based on 100 parts of the vinyl polymer.

[0010] In this application, a cationic polymer with nitrogen-containing functional groups is selected as a coagulant, and the ratio of the cationic polymer to the vinyl polymer is within the above-mentioned range. The resulting coagulated particles have good resistance to heat and oxygen aging, a long oxidation induction period, and a low yellowing index. As an impact modifier, the coagulated particles can effectively improve the impact resistance of the resin composite material. At the same time, the cationic polymer with nitrogen-containing functional groups in the coagulated particles can kill bacteria and fungi through electrostatic interaction, thereby giving the resin composite material good antibacterial and antifungal properties and extending the service life of the resin composite material.

[0011] In this application, the amount of the cationic polymer added is 0.2 to 27 parts, for example, it can be 0.2 parts, 0.5 parts, 1 part, 2 parts, 3 parts, 4 parts, 5 parts, 5.5 parts, 6 parts, 6.5 parts, 7 parts, 7.5 parts, 8 parts, 8.5 parts, 9 parts, 9.5 parts, 10 parts, 10.2 parts, 10.5 parts, 10.8 parts, 11 parts, 11.2 parts, 11.5 parts, 11.8 parts, 12 parts, 12.2 parts, 12.5 parts, etc. 12.8, 13, 13.2, 13.5, 13.8, 14, 14.2, 14.5, 14.8, 15, 15.2, 15.5, 15.8, 16, 16.2, 16.5, 16.8, 17, 17.5, 18, 18.5, 19, 20, 21, 22, 23, 24, 26, and any two of these ranges.

[0012] In this application, the amounts of vinyl polymers and cationic polymers added are both measured by solid mass, i.e., excluding the mass of solvents.

[0013] In one embodiment, based on 100 parts of the vinyl polymer, the amount of the coagulant added is 2 to 18 parts, more preferably 7 to 15 parts.

[0014] In one embodiment, the nitrogen-containing functional group includes at least one of an amide group, an amino group, an ammonium group, a guanidine group, or a nitrogen-containing aromatic group, preferably at least one of an amino group, an ammonium group, or a guanidine group.

[0015] In one embodiment, the cationic polymer includes at least one of chitosan, polyamino acids and their derivatives, polyhexamethylene biguanide and its salts, acrylate polymers containing quaternary ammonium groups, or polycarbonate polymers containing quaternary ammonium groups, more preferably at least one of polyamino acids and their derivatives, polyhexamethylene biguanide and its salts, or acrylate polymers containing quaternary ammonium groups.

[0016] In this application, the "and" in "polyamino acids and their derivatives, polyhexamethylene biguanide and their salts" refers to an and / or relationship, such as polyamino acids and their derivatives including polyamino acids and / or polyamino acid derivatives. The same expression below represents the same meaning.

[0017] In one embodiment, the polyamino acid and its derivatives include at least one of linear homopolymer polyamino acid, linear copolymer polyamino acid, branched homopolymer polyamino acid, branched copolymer polyamino acid, quaternized derivatives of the aforementioned polyamino acid, guanidyl derivatives of the aforementioned polyamino acid, or quaternized and guanidyl derivatives of the aforementioned polyamino acid, and more preferably at least one of the aforementioned quaternized derivatives of the aforementioned polyamino acid, guanidyl derivatives of the aforementioned polyamino acid, or quaternized and guanidyl derivatives of the aforementioned polyamino acid.

[0018] In this application, the "previously mentioned polyamino acid" refers to at least one of the "linear homopolymer polyamino acid, linear copolymer polyamino acid, branched homopolymer polyamino acid, and branched copolymer polyamino acid" mentioned above.

[0019] In one embodiment, the mass percentage of repeating units containing quaternary ammonium groups and / or repeating units containing guanidine groups in the quaternized derivatives, guanidine derivatives, or quaternized and guanidine derivatives of polyamino acids is 50-100%, for example, 50%, 55%, 60%, 65%, 70%, 75%, 80%, 85%, 90%, 95%, 100%, etc.; more preferably 70-100%, and more preferably 90-100%.

[0020] In this application, some or all of the amino groups in the quaternized derivatives, guanidinolated derivatives, or quaternized and guanidinolated derivatives of polyamino acids are converted into quaternary ammonium groups and / or guanidino groups; when the mass percentage of repeating units containing quaternary ammonium groups and / or repeating units containing guanidino groups in the quaternized derivatives, guanidinolated derivatives, or quaternized and guanidinolated derivatives of polyamino acids is 100%, it indicates that all amino groups in the molecular chain are quaternized and / or guanidinolated.

[0021] In one embodiment, the monomers in the linear homopolymeric amino acid and the branched homopolymeric amino acid each independently include any one of lysine, arginine, alanine, isoleucine, phenylalanine, tryptophan, histidine, and glutamine, and are more preferably arginine.

[0022] In one embodiment, the monomers in the linear copolymer polyamino acid and the branched copolymer polyamino acid each independently include at least two of lysine, arginine, alanine, isoleucine, phenylalanine, tryptophan, histidine, and glutamine.

[0023] In this application, the monomers in the linear copolymer polyamino acid and the branched copolymer polyamino acid each independently include at least arginine.

[0024] In this application, the molecular structure of arginine contains a guanidine group. Therefore, compared with other amino acids, the homopolymers or copolymers formed from arginine produce aggregated particles with better heat and oxygen aging resistance. The higher the guanidine group content, the better the aggregated particle performance.

[0025] In this application, the cationic polymer can be obtained commercially or prepared using conventional methods.

[0026] For example, the preparation method of the linear homopolymer polyamino acid or linear copolymer polyamino acid includes: selecting an amino acid containing only one primary amine group and one carboxyl group; mixing an amino acid monomer or its hydrochloride salt with an aqueous solution of an alkaline compound during homopolymerization and copolymerization, wherein the mass ratio of the amino acid monomer or its hydrochloride salt to the aqueous solution of the alkaline compound is (2-5):1; reacting at 200-300°C for 20-50 min under a protective atmosphere; and subjecting the obtained product to precipitation and drying to obtain the linear homopolymer polyamino acid or linear copolymer polyamino acid. The aqueous solution of the alkaline compound includes, but is not limited to, an aqueous solution of potassium hydroxide; the mass fraction of the potassium hydroxide aqueous solution is 10-30 wt%. The difference between the preparation methods of the linear homopolymer polyamino acid and the linear copolymer polyamino acid lies only in the monomer raw materials; when preparing linear homopolymer polyamino acid, the monomer is one type of amino acid monomer; when preparing linear copolymer polyamino acid, the monomer can be equimolar amounts of different amino acid monomers.

[0027] For amino acid monomers containing two or more amino groups, such as lysine, NCA-amino acid monomers (which can be commercially available or self-made) are used as raw materials. The excess amino groups in the amino acid monomer are reacted with groups such as tert-butoxycarbonyl, trifluoroacetyl, or benzyloxycarbonyl to protect the amino groups and prepare NCA-amino acid monomers (N-carboxylic acid anhydride derivatives of amino acids). Then, the NCA amino acid monomers are subjected to ring-opening polymerization. After the reaction is completed, the above groups (tert-butoxycarbonyl, trifluoroacetyl, or benzyloxycarbonyl) are removed by deprotection to obtain the linear homopolymer or linear copolymer of amino acids.

[0028] The ring-opening polymerization method includes: mixing NCA-amino acid monomers with a solvent to obtain an amino acid solution with a concentration of 0.1–0.4 g / mL; mixing an amine compound with a solvent to obtain an amine compound solution with a concentration of 2–20 mg / mL; mixing the amino acid solution and the amine compound solution and stirring at room temperature for 24–96 h; precipitating and drying the resulting reaction mixture to obtain product A; and then deprotecting product A by mixing product A with trifluoroacetic acid to obtain a trifluoroacetic acid solution of product A with a concentration of 0.1 g / mL, adding 0.2–0.6 times the volume of trifluoroacetic acid in an acetic acid solution of hydrogen bromide (hydrogen bromide mass fraction of 20–40 wt%), reacting at room temperature for 1–5 h, then precipitating and drying the product, redissolving the dried solid in water, adjusting the pH to 8–10 with an alkaline compound, and precipitating and drying again to obtain the linear homopolymer polyamino acid or linear copolymer polyamino acid. The amine compounds include, but are not limited to, propylamine; the solvents include, but are not limited to, N,N-dimethylformamide (DMF).

[0029] For example, the preparation method of the branched homopolymer polyamino acid and the branched copolymer polyamino acid can be carried out by the following method:

[0030] An aqueous solution of an amino acid monomer or its hydrochloride salt is mixed with an aqueous solution of an alkaline compound at a mass ratio of (2-5):1. The mixture is reacted at 200-300°C for 20-50 minutes under a protective atmosphere. The resulting product is then precipitated and dried to obtain the branched homopolymer polyamino acid or the branched copolymer polyamino acid. The aqueous solution of the alkaline compound includes, but is not limited to, an aqueous solution of potassium hydroxide. The mass fraction of the potassium hydroxide aqueous solution is 10-30 wt%. The difference between the preparation methods of the branched homopolymer polyamino acid and the branched copolymer polyamino acid lies only in the different monomer raw materials. When preparing the branched homopolymer polyamino acid, the monomer is a single amino acid monomer. When preparing the branched copolymer polyamino acid, the monomer can be an equimolar amount of different amino acid monomers.

[0031] Exemplarily, the preparation method of the quaternized derivative of the polyamino acid includes: mixing the polyamino acid with a quaternizing agent and a solvent to obtain a reaction solution; wherein the mass ratio of the polyamino acid to the quaternizing agent in the reaction solution is (1-4):1, and the total concentration of the polyamino acid and the quaternizing agent in the reaction solution is 0.02-0.1 g / mL; reacting the reaction solution at 30-60°C for 12-36 h, settling, and drying to obtain the quaternized derivative of the polyamino acid; wherein the polyamino acid includes linear homopolymer polyamino acid, linear copolymer polyamino acid, branched homopolymer polyamino acid, or branched copolymer polyamino acid; the quaternizing agent includes compounds containing an acrylamide group and / or an ammonium group, such as N,N-dimethyl-N-alkylacrylamide compounds, wherein the alkyl group can be a C7-C18 straight-chain or branched alkyl group; or, (2-acrylamidoethyl)ammonium salt with different substituents on N, wherein the substituents include C1-C10 straight-chain or branched alkyl groups.

[0032] For example, the method for preparing the guanidinolated derivative of the polyamino acid includes the following steps:

[0033] A guanidinizing agent, potassium carbonate, and an aqueous solution of a polyamino acid (the polyamino acid mass fraction is 1-4 wt%) are mixed to obtain a reaction solution (in which the molar amounts of the guanidinizing agent and potassium carbonate are equal). The degree of guanidinization modification of the polyamino acid can be adjusted by regulating the mass ratio (or molar ratio) of the guanidinizing agent to the polyamino acid. The reaction solution is reacted at 40-80°C for 6-24 hours under a protective atmosphere, followed by precipitation and drying to obtain the guanidinized derivative of the polyamino acid. The polyamino acid includes linear homopolymer polyamino acid, linear copolymer polyamino acid, branched homopolymer polyamino acid, or branched copolymer polyamino acid. The guanidinizing agent includes 1H-pyrazole-1-formamidinium hydrochloride, methoxyisourea (or its sulfate), sodium 2-ethyl-2-thiourea hydrobromide, etc.

[0034] For example, the preparation method of the acrylate polymer containing quaternary ammonium groups can be carried out using a reversible addition-fragmentation chain transfer polymerization (RAFT polymerization) method; specifically, the method includes:

[0035] An acrylate monomer is mixed with an initiator, a chain transfer agent, and a solvent to obtain a reaction solution (the initiator is 0.05–1.5 wt% of the total mass of the acrylate monomers, the chain transfer agent is 5–20 wt% of the total mass of the acrylate monomers, and the total mass concentration of the acrylate monomers, initiator, and chain transfer agent in the reaction solution is 180–240 mg / mL); the reaction solution is reacted at 60–90 °C for 4–12 h under a protective atmosphere, and after sedimentation, centrifugation, and drying, the acrylate polymer is obtained; the acrylate monomer is an acrylate containing amino, ammonium, pyridine, pyrrole, pyrazole, or indole residues, or an acrylate containing the above groups can be obtained by simple treatment after polymerization, including but not limited to any one or at least a combination of two of (meth)acrylate aminoethyl ester and its salts, and (meth)acrylate-2-indoleethyl ester. The initiators include, but are not limited to, azo initiators and / or organic peroxide initiators; the azo initiators include, but are not limited to, azobisisobutyronitrile (AIBN); the peroxide initiators include, but are not limited to, benzoyl peroxide (BPO). The chain transfer agents include, but are not limited to, dithioester derivatives, including, but are not limited to, cumyl dithiobenzoate (CDB), 2-cyano-2-propyldodecyl trithiocarbonate, 2-cyano-2-propylbenzodisulfide, 2-phenylpropane thiobenzoate, 2-(dodecyltrithiocarbonate)-2-methylpropionic acid, and 4-cyano-4-[(dodecylthioalkylthiocarbonyl)thioalkyl]valerate, etc. The solvents in the RAFT polymerization include, but are not limited to, dimethyl sulfoxide (DMSO).

[0036] For example, the method for preparing the polycarbonate containing quaternary ammonium groups includes:

[0037] Functionalized cyclic carbonate monomers were mixed with catalyst 1 and a solvent to obtain mixture 1 (catalyst 1 accounted for 2-8 wt% of the functionalized cyclic carbonate monomers, and the total mass concentration of the catalyst and functionalized cyclic carbonate monomers was 200-300 mg / mL). Mixture 1 was then mixed with an alcohol initiator (added at 0.8-2.5 wt% of the functionalized cyclic carbonate monomers) and catalyst 2 (added at 1-3 wt% of the alcohol initiator). After stirring at room temperature for 10-60 min, [further steps were taken]. The catalyst is quenched by adding excess benzoic acid; the resulting reaction product is then precipitated to obtain a white solid; the white solid is then mixed with a solvent (e.g., acetonitrile) to obtain a polycarbonate solution (polycarbonate mass concentration of 0.015–0.05 g / mL); the polycarbonate solution is mixed with a quaternizing agent (molar ratio of polycarbonate to quaternizing agent of 1:5–15), stirred at room temperature for 8–24 h, and the resulting product is purified and dried to obtain polycarbonate containing quaternary ammonium groups; the functionalized The cyclic carbonate monomer can be a six-membered cyclic acetal compound containing amino, ammonium, pyridine, pyrrole, pyrazole, or indole residues, or can be obtained by simple treatment after polymerization, including but not limited to 2,2-dihydroxymethylformaldehyde propionate compounds; the catalyst 1 includes compounds containing thiourea groups, including but not limited to N-(3,5-trifluoromethylbenzene)-N′-cyclohexylthiourea (1-(3,5-bis(trifluoromethyl)-phenyl)-3-cyclohexyl-2-thiourea); the alcohol initiator can be a monohydric alcohol or a polyhydric alcohol, including but not limited to 4-methylbenzyl alcohol; the catalyst 2 includes an organic base, including but not limited to dicycloamidinium; the purification method includes but is not limited to dialysis; the drying method includes but is not limited to freeze drying; the quaternizing agent includes but is not limited to N-alkylammonium, wherein the alkyl group can be a saturated alkane or an unsaturated alkane with a chain length of C1 to C18, such as N-dimethylhexylammonium chloride.

[0038] In one embodiment, the molecular structure of the vinyl polymer includes any one or a combination of at least two of the following: structural units derived from conjugated dienes, structural units derived from styrene and its derivatives, structural units derived from acrylonitrile and its derivatives, or structural units derived from alkyl (meth)acrylates.

[0039] In one embodiment, the molecular structure of the vinyl polymer includes structural units derived from conjugated dienes and structural units derived from styrene and its derivatives, and also includes at least one of structural units derived from acrylonitrile and its derivatives and structural units derived from alkyl (meth)acrylates.

[0040] In one embodiment, the mass percentage of structural units derived from conjugated dienes in the vinyl polymer is 50-80%, for example, it can be a range of 50%, 52%, 54%, 56%, 58%, 60%, 62%, 64%, 66%, 68%, 70%, 72%, 72.5%, 73%, 73.5%, 74%, 74.5%, 75%, 75.5%, 76%, 76.5%, 77%, 77.5%, 78%, 78.5%, 79%, 79.5%, 80%, and any combination thereof; preferably 55-78%, more preferably 60-75%; the mass percentage of structural units derived from styrene and its derivatives is 5-25%, for example, it can be 5%, 5.5%, 6%, etc. The range of values ​​consisting of 6.5%, 7%, 7.5%, 8%, 8.5%, 9%, 9.5%, 10%, 10.5%, 11%, 11.5%, 12%, 12.5%, 13%, 13.5%, 14%, 14.5%, 15%, 15.5%, 16%, 16.5%, 17%, 17.5%, 18%, 18.5%, 19%, 19.5%, 20%, 20.5%, 21%, 21.5%, 22%, 22.5%, 23%, 23.5%, 24%, 24.5%, 25%, and any combination thereof; preferably 11-20%, more preferably 12-18%; the balance being structural units derived from acrylonitrile and its derivatives, and / or structural units derived from alkyl (meth)acrylates.

[0041] In this application, the mass percentage of each structural unit in the vinyl polymer is expressed as the mass percentage of each monomer in the total monomers. For example, the mass percentage of structural units derived from conjugated dienes in the vinyl polymer is 50-80%, which means that the conjugated diene monomer accounts for 50-80% of the total monomer mass.

[0042] In this application, the conjugated diene includes conjugated dienes with ≥4 carbon atoms, exemplarily including butadiene, isoprene, hexadiene, heptaadiene, nonadiene, etc.; the styrene and its derivatives include, but are not limited to, any one or a combination of at least two of styrene, α-ethylstyrene, α-methylstyrene, p-methylstyrene, o-tert-butylstyrene, bromostyrene, or chlorostyrene (such as trichlorostyrene); acrylonitrile and its derivatives include, but are not limited to, acrylonitrile, methacrylonitrile, fumaric acid, etc. The alkyl (meth)acrylates include, but are not limited to, methyl methacrylate, methyl acrylate, butyl methacrylate, butyl acrylate, etc.

[0043] In this application, the vinyl polymers include at least one of butadiene-styrene-acrylonitrile copolymer (ABS), butadiene-methyl methacrylate-styrene-acrylonitrile copolymer (MABS), butadiene-methyl methacrylate-styrene copolymer (MBS), or acrylonitrile-styrene-acrylate monomer copolymer (ASA).

[0044] In this application, when the vinyl polymer is an acrylonitrile-styrene-acrylate monomer copolymer, the mass percentage of the structural unit derived from (meth)acrylate alkyl ester is 50-85%.

[0045] In one embodiment, the oxidation induction period of the condensed particles in an air atmosphere under isothermal conditions of 200°C is ≥30 min, preferably ≥35 min, and more preferably ≥40 min.

[0046] In one embodiment, the condensed particles have a b-value of ≤10, preferably ≤8, and more preferably ≤5, as measured by a Lab colorimeter.

[0047] In this application, the condensed particles have a low water content, which is <0.25%.

[0048] In this application, the moisture content (in terms of mass percentage) of the agglomerated particles is tested in accordance with the method specified in GB / T 2914-2008 "Determination of volatiles (including water) in homopolymer copolymer resins of vinyl chloride".

[0049] Secondly, this application provides a method for preparing condensed particles according to the first aspect, the method comprising the following steps:

[0050] The latex of a vinyl polymer is mixed with a coagulant, and then coagulated and dried to obtain the coagulated particles.

[0051] In this application, the latex of the vinyl polymer (solid content of 30-60%) can be obtained commercially or prepared by conventional methods. Exemplarily, the preparation method includes the following steps:

[0052] (1) The solvent, initiator, chain transfer agent, electrolyte, emulsifier and 20% of the surfactant in the formulation are mixed evenly at room temperature. Under the presence of a protective atmosphere, the conjugated diene monomer is added to it. After reacting at 50-60℃ and 100-110rpm for 6-12h, the temperature is raised to 65-75℃ and the speed is raised to 110-125rpm for 8-16h. The temperature is then raised to 70-80℃ and the speed is raised to 135-135rpm for 8-16h. Then, the remaining surfactant is added to it, and after stirring for 20-40min, the mixture is cooled and discharged to obtain polyconjugated diene latex.

[0053] (2) The polyconjugated diene latex obtained in step (1), initiator, chain transfer agent, emulsifier, catalyst, solvent and graft monomer (graft monomer includes at least two of styrene and its derivatives, acrylonitrile and its derivatives, and alkyl (meth)acrylate) are mixed and reacted at 50-60°C for 1-6 hours. Then, a surfactant is added and the reaction continues for 0.5-3 hours to obtain the latex of the vinyl polymer.

[0054] In step (1) of the preparation method, the solvent includes water; the mass of the solvent is 80-120 parts per 100 parts of the conjugated diene monomer; the initiator can be a commonly used initiator, including but not limited to one or more of potassium persulfate, ammonium persulfate, or sodium persulfate; the mass of the initiator is 0.1-1 parts per 100 parts of the conjugated diene monomer; the chain transfer agent can be a commonly used chain transfer agent, including but not limited to n-dodecyl mercaptan and / or tert-dodecyl mercaptan; the mass of the chain transfer agent is 0.2-1.2 parts per 100 parts of the conjugated diene monomer; the electrolyte can be a commonly used electrolyte, including but not limited to one or more of sodium carbonate, sodium bicarbonate, sodium hydroxide, potassium carbonate, or potassium hydroxide; the mass of the initiator is 80-120 parts per 100 parts of the conjugated diene monomer ... The electrolyte comprises 0.1 to 1 part per 100 parts; the emulsifier may be a commonly used emulsifier, including anionic emulsifiers; the anionic emulsifier includes, but is not limited to, one or more of disproportionated rosin acid soap, stearic acid soap, oleic acid soap, tallow fatty acid soap, lauric acid soap, alkylbenzene sulfonate, and sulfate ester salt; the emulsifier comprises 0.1 to 1 part per 100 parts of the conjugated diene monomer; the surfactant includes alkynyl alcohol surfactants, which can act as emulsifiers, and may be a commonly used alkynyl alcohol surfactant, including, but not limited to, one or more of methylpentynyl alcohol, 2,4,7,9-tetramethyl-5-decyn-4,7-diol, and ethyloctynyl alcohol; the total mass of the surfactant comprises 0.1 to 1 part per 100 parts of the conjugated diene monomer.

[0055] In step (2) of the preparation method, the initiator, chain transfer agent, emulsifier, surfactant, and solvent are selected from the same range as those in step (1); and the types of components in steps (1) and (2) are the same or different; based on 100 parts of the dry mass of polyconjugated diene latex, the mass of each of the initiator, chain transfer agent, emulsifier, and surfactant is independently 0.1 to 1 part; the catalyst can be a commonly used catalyst, including but not limited to tetramethylethylenediamine and / or sodium formaldehyde sulfoxylate; based on 100 parts of the dry mass of polyconjugated diene latex, the mass of the catalyst is 0.2 to 2 parts, and the mass of the solvent is 100 to 140 parts.

[0056] In one implementation, the condensation occurs under neutral conditions.

[0057] In this application, the neutral condition is adjusted by adding a pH adjuster, which includes organic acids and / or inorganic acids; the functionality of the organic acids and / or inorganic acids is 1 to 3, preferably sulfuric acid and / or acetic acid.

[0058] In this application, the mixing is carried out in a solvent, which includes water; the specific steps of the mixing include: adjusting the latex of the vinyl polymer to neutral using a pH adjuster; premixing the cationic polymer with the solvent to obtain a coagulated liquid with a solid content of 4-10%; and then mixing the coagulated liquid with the latex of the vinyl polymer at 50-95°C according to a formulation in which the ratio of vinyl polymer to cationic polymer is 100:0.2-27 (both vinyl polymer and cationic polymer are based on solid weight).

[0059] In this application, the solid content of the coagulated liquid is selected so that the cationic polymer can be fully dissolved, resulting in a solution with a low concentration and good fluidity.

[0060] In one embodiment, the coagulation includes coagulation through a first heat preservation, a heating, a second heat preservation, and a cooling.

[0061] In one embodiment, the temperature of the first heat preservation is 70-80°C, for example, 70°C, 72°C, 74°C, 75°C, 76°C, 78°C, 80°C, etc.; the time is 1-10 min, for example, 1 min, 2 min, 3 min, 4 min, 5 min, 6 min, 7 min, 8 min, 9 min, 10 min, etc.

[0062] In one embodiment, the heating rate is 3 to 7 °C / min, for example, it can be 3 °C / min, 4 °C / min, 5 °C / min, 6 °C / min, 7 °C / min, etc.

[0063] In one embodiment, the temperature of the second heat preservation is 90-100°C, for example, it can be 90°C, 91°C, 92°C, 93°C, 94°C, 95°C, 96°C, 97°C, 98°C, 99°C, 100°C, etc.; the time is 5-15 minutes, for example, it can be 5 minutes, 6 minutes, 7 minutes, 8 minutes, 9 minutes, 10 minutes, 11 minutes, 12 minutes, 13 minutes, 14 minutes, 15 minutes, etc.

[0064] In one embodiment, the cooling rate is 0.5 to 4 °C / min, for example, it can be 0.5 °C / min, 1 °C / min, 1.5 °C / min, 2 °C / min, 2.5 °C / min, 3 °C / min, 3.5 °C / min, 4 °C / min, etc.; until the temperature drops to room temperature.

[0065] In this application, the process before drying further includes solid-liquid separation of the coagulated slurry; this solid-liquid separation can be achieved through methods such as filtration, centrifugal dehydration, or spray drying. To improve the whiteness of the coagulated powder, the dehydrated powder can be washed. The drying step can be hot air drying on a fluidized bed at a temperature of 50–70°C; or it can be dehydration by extrusion on a wet extruder.

[0066] Thirdly, this application provides a resin composition, which, by weight, comprises 70 to 90 parts of resin (e.g., a range of 70, 72, 74, 76, 78, 80, 82, 84, 86, 88, 90 parts, or any combination thereof) and 10 to 30 parts of impact modifier (e.g., a range of 10, 12, 14, 16, 18, 20, 22, 24, 26, 28, 30 parts, or any combination thereof); the impact modifier comprises the cohesive particles described in the first aspect.

[0067] In this application, the agglomerated particles can serve as a good impact modifier, and can be blended and kneaded with other resin materials to form a resin composition. The impact strength of this resin composition can be increased with the increase of the agglomerated particle content. Simultaneously, the cationic polymer contained in the latex agglomerated particles has certain antibacterial properties, enabling the agglomerated particles and the compositions obtained by blending them with certain resin materials to also possess good antibacterial and antifungal effects.

[0068] In this application, the resin includes at least one of styrene-acrylonitrile copolymer, polymethyl methacrylate, methyl methacrylate-styrene-acrylonitrile terpolymer, polystyrene, polyvinyl chloride, polycarbonate, polypropylene, polyphenylene ether, polyester, or polyamide.

[0069] In one embodiment, the resin composition has an antibacterial rate of ≥80%, preferably ≥90%, more preferably ≥95%, and particularly preferably ≥99.9%; and a mildew resistance level of 0-1.

[0070] In one embodiment, the notched cantilever beam impact strength of the resin composition is ≥24 kJ / m. 2 Preferred ≥28kJ / m 2 More preferably ≥30kJ / m 2 .

[0071] 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.

[0072] Compared with the prior art, the beneficial effects of this application are as follows:

[0073] The coagulated particles provided in this application use a cationic polymer with nitrogen-containing functional groups as a coagulant, and the ratio of the cationic polymer to the vinyl polymer is within a specific range. The resulting coagulated particles have good heat and oxygen aging resistance, a long oxidation induction period, and a low yellowing index. As an impact modifier, the coagulated particles can effectively improve the impact resistance, heat oxidation resistance, and aging and yellowing resistance of resin composites. At the same time, they give the resin composites excellent antibacterial and antifungal properties, extending the service life of the resin composites.

[0074] After reading and understanding the detailed description, other aspects can be understood. Detailed Implementation

[0075] The technical solution of this application will be further described below through specific embodiments. Those skilled in the art should understand that the embodiments described are merely to help understand this application and should not be regarded as specific limitations on this application.

[0076] Preparation Example 1: Preparation of latex of vinyl polymer (A)

[0077] Vinyl polymer A1 latex

[0078] By mass percentage, the molecular structure of the vinyl polymer A1 includes 68% structural units derived from butadiene, 15% structural units derived from styrene, and 17% structural units derived from acrylonitrile.

[0079] The method for preparing the latex of the vinyl polymer A1 includes:

[0080] Step S1: By weight, add 100 parts water, 0.4 parts ammonium persulfate, 0.6 parts n-dodecyl mercaptan, 0.4 parts sodium carbonate, 0.4 parts potassium stearate, and 0.08 parts ethyl octyne alcohol to a reactor and stir at room temperature until completely dissolved and mixed evenly. Purge the reactor with nitrogen to replace the air, so that the oxygen content is below 10 ppm. Then add 100 parts butadiene monomer according to the formula. Heat the reactor to 55°C and keep it at that temperature for 9 hours for the first stage of polymerization, and control the stirring speed at 105 rpm. After the first stage of polymerization, heat the system to 70°C and keep it at that temperature for 12 hours for the second stage of polymerization, and control the stirring speed at 120 rpm. After the second stage of polymerization, heat the system to 75°C and keep it at that temperature for 12 hours for the third stage of polymerization, and control the stirring speed at 130 rpm. At the end of the polymerization reaction, add 0.32 parts ethyl octyne alcohol, stir for half an hour, cool down and discharge the material to obtain polybutadiene latex.

[0081] Step S2: Heat the polybutadiene latex from step S1 to 55°C. Based on 100 parts of dry polybutadiene latex, add 0.4 parts of potassium persulfate, 0.6 parts of tert-dodecyl mercaptan, 0.4 parts of potassium oleate, 1 part of tetramethylethylenediamine, and 120 parts of water. Add the formulated amounts of acrylonitrile monomer and styrene monomer. Add dropwise continuously for 2 hours. After the addition is complete, continue the reaction for 3 hours. Then add 0.4 parts of ethyl octyryne alcohol and continue the reaction at 55°C for 2 hours. After cooling to room temperature, the latex of the vinyl polymer A1 is obtained, with a solid content of approximately 32%.

[0082] Vinyl polymers A2 to A7 latex

[0083] The preparation methods of latex for vinyl polymers A2 to A7 are the same as those for vinyl polymer A1. The only difference is that the types and masses of each structural unit of the vinyl polymer are different, that is, the types and proportions of monomers are different (the total amount of monomers is the same). The specific formulations are shown in Table 1, based on the mass percentage (total amount of monomers is 100%). In the table, " / " indicates that the component is not in the formulation.

[0084] Table 1

[0085] Preparation Example 2: Preparation of Cationic Polymer (B)

[0086] Cationic polymer B1

[0087] Linear poly-ε-lysine: purchased from Aladdin, product number P303210-25g;

[0088] Cationic polymer B2

[0089] Linear poly-α-lysine

[0090] The preparation method includes: dissolving 10g of Nε-benzyloxycarbonyl-L-lysine intracyclic anhydride (purchased from Sichuan Jiayinglai Technology Co., Ltd.) monomer in 45mL of anhydrous N,N-dimethylformamide (DMF), then adding 5mL of a 10mg / mL propylamine DMF solution, stirring at room temperature for 72h, precipitating the resulting reaction mixture in diethyl ether, and drying under vacuum to obtain a white powder (8.47g). Then, dissolving 7.5g of the white powder in 75mL of trifluoroacetic acid, adding 30mL of a 33wt% hydrogen bromide acetic acid solution, and reacting at room temperature for 3h. Precipitation with diethyl ether followed by adding water to the precipitate and rotary evaporation for drying. The resulting solid is dissolved in water, adjusted to pH 9 with sodium hydroxide, then precipitated with diethyl ether, and dried under vacuum to obtain linear polyα-lysine.

[0091] Cationic polymer B3

[0092] Branched polylysine

[0093] The preparation method includes: adding 91.32g of lysine hydrochloride and 28.05g of KOH solution (20wt%) into a 500mL round-bottom flask, connecting a water separator, purging nitrogen three times for more than 10 minutes each time, and finally maintaining a nitrogen atmosphere. After stirring and heating at 250℃ for 30 minutes, the heating is stopped, the obtained product is dissolved in methanol and precipitated into diethyl ether, and then dried under vacuum to obtain branched polylysine.

[0094] Cationic polymer B4

[0095] Partially guanidine-modified linear poly-α-lysine (the mass of the repeating unit containing the guanidine group accounts for 50% of the total mass of the partially guanidine-modified linear poly-α-lysine)

[0096] The preparation method includes: guanidinizing some primary amines in linear poly-α-lysine using a guanidinizing agent to obtain partially guanidinated linear poly-α-lysine. Specifically, the preparation method involves adding 0.73 g of 1H-pyrazole-1-formamidinium hydrochloride and 0.69 g of potassium carbonate to 80 g of an aqueous solution containing 2.5 wt% linear poly-α-lysine; after purging with nitrogen three times, the mixed solution is heated at 60 °C for 12 h, then precipitated with diethyl ether and dried under vacuum to obtain partially guanidinated linear α-lysine. The repeating units containing amino groups and repeating units containing guanidin groups are randomly distributed in the polymer chain segments at a mass ratio of 1:1.

[0097] Cationic polymer B5

[0098] A copolymer of branched lysine and arginine

[0099] The only difference between the preparation method and the preparation method of branched polylysine is that 91.32g of lysine hydrochloride is replaced with an equal mass of a mixed monomer of lysine hydrochloride and arginine (molar ratio of 1:1). All other steps are the same.

[0100] Cationic polymer B6

[0101] Linear poly-α-lysine quaternary ammonium salt

[0102] The preparation method includes: dissolving 5g of N,N-dimethyldodecyl(2-acrylamidoethyl)ammonium bromide in 200mL of deionized water, adding 10g of linear poly-α-lysine, reacting at 40℃ for 24h, precipitating the resulting reaction mixture in diethyl ether, centrifuging to obtain a yellow solid, dissolving it in water and then freeze-drying it to obtain linear poly-α-lysine quaternary ammonium salt.

[0103] Cationic polymer B7

[0104] Branched lysine quaternary ammonium salt

[0105] The only difference between the preparation method and the preparation method of linear poly-α-lysine quaternary ammonium salt is that 10g of linear poly-α-lysine is replaced with an equal mass of branched poly-lysine; all other steps are the same.

[0106] Cationic polymer B8

[0107] The preparation method of guanidinolated branched polylysine includes: adding 1.46 g of 1H-pyrazole-1-formamidinium hydrochloride and 1.38 g of potassium carbonate to 80 g of an aqueous solution containing 2.5 wt% branched polylysine; after purging with nitrogen three times, heating the mixed solution at 60 °C for 12 h, then precipitating with diethyl ether and drying under vacuum to obtain guanidinolated branched polylysine, which belongs to the guanidinolated derivatives of branched polyamino acids.

[0108] Cationic polymer B9

[0109] Polyhexamethylene biguanide hydrochloride: purchased from Maclean's, product number P832584.

[0110] Cationic polymer B10

[0111] Copolymer P(AEMA-co-IEMA) of aminoethyl methacrylate and 2-indoleethyl methacrylate

[0112] The preparation method includes: dissolving 331 mg of 2-aminoethylmethacrylate (AEMA), 229 mg of 2-(1H-indol-3-yl)ethyl methacrylate (IEMA), 7 mg of azobisisobutyronitrile (AIBN), and 81 mg of chain transfer agent 4-cyano-4-[(dodecylthioalkylthiocarbonyl)thioalkyl]valerate in 3 mL of dimethyl sulfoxide (DMSO), and then dissolving the solution under high vacuum (1000 ppm). -3 The reaction was carried out under Torr (Temperature) for three cycles of freezing-extraction-thawing, followed by heating to 70°C and reacting for 8 hours. The resulting product was purified by three precipitations with methanol-diethyl ether, centrifuged three times, and dried to obtain a copolymer of aminoethyl methacrylate and 2-indoleethyl methacrylate, which belongs to the acrylate copolymers containing quaternary ammonium groups.

[0113] Cationic polymer B11

[0114] Polycarbonate containing quaternary ammonium groups

[0115] The preparation method includes: using a glove box, mixing 448 mg of the functionalized cyclocarbonate monomer 2,2-bis(trifluoromethyl)-propionic acid p-chloromethylbenzyl alcohol (MTC-OCH2BnCl), 22.2 mg of N-(3,5-trifluoromethylbenzene)-N′-cyclohexylthiourea (1-(3,5-bis(trifluoromethyl)-phenyl)-3-cyclohexyl-2-thiourea) with 2 mL of dry dichloromethane, then adding 7.32 mg of 4-methylbenzyl alcohol, followed by 8.96 μL of bicycloamidine, and stirring at room temperature for about 30 min. Then, excess benzoic acid (10 mg) was added to quench the catalyst. The resulting crude product was precipitated twice in cold methanol, and the supernatant was decanted to obtain polycarbonate. The polycarbonate was then quaternized by dissolving 0.35 g of polycarbonate in 10 mL of acetonitrile, adding an excess of quaternizing agent (N-dimethylhexylammonium chloride), and stirring the reaction mixture overnight at room temperature. After quaternization, the crude product was purified by dialysis using a 1:1 acetonitrile and isopropanol solvent system. After solvent removal, the resulting polymer was freeze-dried to obtain polycarbonate containing quaternary ammonium groups.

[0116] Cationic polymer B12

[0117] Chitosan: Purchased from Maclean's, product number C850346.

[0118] Cationic polymer B13

[0119] Polyacrylamide: purchased from Sigma-Aldrich, item number 738743.

[0120] The condensed particles provided in this application all have a moisture content of 0.2%.

[0121] Example 1

[0122] This embodiment provides a coagulated particle, which includes a vinyl polymer A1 and a cationic polymer B6; with 100 parts of vinyl polymer A1 added, the amount of cationic polymer B6 added is 8.5 parts, and the parts are calculated based on the dry basis of the vinyl polymer and the dry basis of the cationic polymer.

[0123] This embodiment provides a method for preparing condensed particles, including the following steps:

[0124] Cationic polymer B6 was mixed with water to obtain a cationic polymer aqueous solution with a solid content of 4.3%. The latex of vinyl polymer A1 was adjusted to neutral with concentrated sulfuric acid. Then, at 75°C, the latex of vinyl polymer A1 was added to the cationic polymer aqueous solution in four portions, each time accounting for 25% of the total latex volume. The resulting mixture was then maintained at 75°C for 5 minutes, and the temperature was increased to 95°C at a rate of 5°C / min and maintained for 10 minutes. The temperature was then reduced to room temperature at a rate of 2°C / min to obtain a coagulated slurry. The coagulated slurry was dehydrated by a centrifugal dewatering machine and then dried on a fluidized bed at 60°C to obtain the coagulated particles.

[0125] Examples 2-24, Comparative Examples 1-4

[0126] Examples 2-24 and Comparative Examples 1-4 each provide a coagulated particle, differing from Example 1 only in the type of vinyl polymer, the type of coagulant, and their content. Specific formulations are shown in Tables 2, 3, 4, and 5, where " / " indicates that the component is not in the formulation. Specifically, for Example 23, to improve the solubility of the cationic polymer B12, a 2% (w / w) aqueous solution of acetic acid was used to prepare a cationic polymer aqueous solution of the same concentration. Comparative Example 3 used concentrated sulfuric acid as the coagulant, which could not completely demulsify; during solid-liquid separation, the liquid portion still contained a large amount of latex, and the aqueous phase was milky white. Only the portion that had been coagulated and demulsified was used. In contrast, the other examples and comparative examples completely demulsified during the coagulation process, and the aqueous layer during solid-liquid separation was a clear, transparent yellow to light yellow solution.

[0127] Table 2

[0128] Table 3

[0129] Table 4

[0130] Table 5

[0131] Application examples

[0132] This application example provides a resin composition comprising, by weight, 20 parts of an impact modifier and 80 parts of SAN resin (resin brand name KFA-130, Liaoning Jinfeng); the impact modifier being the cohesive particles provided in Examples 1-24 and Comparative Examples 1-4.

[0133] Control group 1: In this application, SAN resin without added coagulated particles (resin brand name KFA-130, Liaoning Jinfeng) was used as control group 1.

[0134] Performance testing

[0135] (1) Oxidation Induction Period (OIT): The oxidation induction period of the aggregated particles was tested, referring to the determination in the national standard GB / T19466.6-2009 "Differential Scanning Calorimetry (DSC) for Plastics - Part 6: Oxidation Induction Time (Isothermal OIT) and Oxidation Induction Temperature (Dynamic OIT)". Specifically, the OIT was tested under isothermal conditions of 200℃ in an air atmosphere.

[0136] (2) Heat aging and yellowing resistance: The dried aggregated particles were placed in multiple aluminum foil petri dishes and placed in a constant temperature oven at 180℃. After 24 hours of constant temperature, the samples were taken out and the b value of the aggregated particles was tested using a Lab colorimeter. The larger the b value, the worse the heat aging and yellowing resistance.

[0137] (3) Impact resistance: The resin composition including the agglomerated particles is mixed with a twin-screw extruder, and the resin composition is injection molded into a notched standard specimen according to the requirements of GB / T 1843-2008 Determination of cantilever beam impact strength of plastics and its cantilever beam notched impact strength is tested.

[0138] (4) Antibacterial and antifungal properties: The resin composition including the aggregated particles was mixed with a twin-screw extruder and pressed into sheets at an upper and lower plate temperature of 200°C on a flat vulcanizer to prepare sheets with a thickness of (50±2)mm×(50±2)mm and not exceeding 10mm. The antibacterial and antifungal properties of the resin composition were tested.

[0139] The antibacterial performance was tested according to the national standard GB / T 31402-2015 "Test Method for Antibacterial Properties of Plastic Surfaces - Antibacterial Properties of Materials". Specifically, the antibacterial test adopted the film-coating method, and the operation steps were as follows: After the sample was disinfected, a bacterial suspension was inoculated on its surface and covered with a polyethylene film to form a uniform liquid film between the sample and the film. After incubation under certain conditions, the suspension was washed off and diluted to an appropriate concentration gradient. A certain volume was taken and spread on the culture medium for re-incubation, and the number of viable bacteria was measured to calculate the antibacterial rate. The antibacterial rate was calculated using the formula: Antibacterial rate % = (Number of bacteria in a pure resin sample after 24 hours - Number of bacteria in the corresponding example or comparative sample after 24 hours) / Number of bacteria in a pure resin sample after 24 hours * 100%. The bacteria used for testing was *Escherichia coli* ATCC 25922.

[0140] The anti-mildew performance was tested in accordance with the national standard GB21551.2-2010 "Special requirements for antibacterial materials with antibacterial, sterilization and purification functions for household and similar electrical appliances"; where 0 indicates the highest level of anti-mildew resistance and 3 indicates the lowest level of anti-mildew resistance.

[0141] The specific test results are shown in Table 6, where "-" indicates that no test was performed.

[0142] Table 6

[0143] In summary, the coagulated particles provided in this application utilize a cationic polymer with nitrogen-containing functional groups as a coagulant, and the ratio of the cationic polymer to the vinyl polymer is within a specific range. The resulting coagulated particles exhibit excellent resistance to heat and oxygen aging, a long oxidation induction period, and a low yellowing index. As an impact modifier, these coagulated particles effectively improve the impact resistance, heat oxidation resistance, and aging and yellowing resistance of resin composites. Simultaneously, they impart excellent antibacterial and antifungal properties to the resin composites. The latex coagulated particles exhibit an oxidation induction period ≥30 min under air atmosphere and isothermal conditions of 200°C. Furthermore, after continuous baking at 180°C for 24 h in an oven, they are whiter than the coagulated particles obtained in the comparative example, with a b-value less than 10. The resin composition including these coagulated particles has a notched cantilever beam impact strength greater than 24 kJ / m. 2 Furthermore, its antibacterial rate reaches over 80%, and its anti-mildew level is 0-1.

[0144] The specific embodiments described above further illustrate the purpose, technical solution, and beneficial effects of this application. It should be understood that the above descriptions are merely specific embodiments of this application and are not intended to limit this application. Any modifications, equivalent substitutions, improvements, etc., made within the spirit and principles of this application should be included within the protection scope of this application.

Claims

1. A coagulating particle comprising a vinyl polymer and a coagulant; wherein The coagulant includes a cationic polymer; The molecular structure of the cationic polymer contains nitrogen-containing functional groups; Based on an addition amount of 100 parts of the vinyl polymer, the addition amount of the cationic polymer is 0.2 to 27 parts; The nitrogen-containing functional group includes at least one of an amide group, an amino group, an ammonium group, a guanidine group, or a nitrogen-containing aromatic group; The molecular structure of the vinyl polymer includes any one or a combination of at least two of the following: structural units derived from conjugated dienes, structural units derived from styrene and its derivatives, structural units derived from acrylonitrile and its derivatives, or structural units derived from alkyl (meth)acrylates.

2. The coacervate particle of claim 1, wherein, Based on an addition amount of 100 parts of the vinyl polymer, the addition amount of the coagulant is 2 to 18 parts.

3. The coacervate particle of claim 1, wherein, The cationic polymer includes at least one of chitosan, polyamino acids and their derivatives, polyhexamethylene biguanide and its salts, acrylate polymers containing quaternary ammonium groups, or polycarbonate polymers containing quaternary ammonium groups. The polyamino acids and their derivatives include at least one of linear homopolymer polyamino acids, linear copolymer polyamino acids, branched homopolymer polyamino acids, branched copolymer polyamino acids, quaternized derivatives of the aforementioned polyamino acids, guanidineized derivatives of the aforementioned polyamino acids, or quaternized and guanidineized derivatives of the aforementioned polyamino acids. The quaternized derivatives of polyamino acids, guanidinated derivatives of polyamino acids, or quaternized and guanidinated derivatives of polyamino acids contain repeating units with quaternary ammonium groups and / or repeating units with guanidinium groups at a mass percentage of 50-100%. The monomers in the linear homopolymer polyamino acids and branched homopolymer polyamino acids each independently include any one of lysine, arginine, alanine, isoleucine, phenylalanine, tryptophan, histidine, and glutamine. The monomers in the linear copolymer polyamino acid and the branched copolymer polyamino acid each independently include at least two of the following: lysine, arginine, alanine, isoleucine, phenylalanine, tryptophan, histidine, and glutamine. The monomers in the linear copolymer polyamino acid and the branched copolymer polyamino acid each independently include at least arginine.

4. The coacervate particle of claim 1, wherein, The molecular structure of the vinyl polymer includes structural units derived from conjugated dienes and structural units derived from styrene and its derivatives, and also includes at least one of structural units derived from acrylonitrile and its derivatives and structural units derived from alkyl (meth)acrylates. In the vinyl polymer, the mass percentage of structural units derived from conjugated dienes is 50-80%, the mass percentage of structural units derived from styrene and its derivatives is 5-25%, and the balance is structural units derived from acrylonitrile and its derivatives, and / or structural units derived from alkyl (meth)acrylates.

5. The coacervate particle of claim 1, wherein, The oxidation induction period of the condensed particles under air atmosphere and isothermal conditions of 200°C is ≥30 min; The condensed particles, measured using a Lab colorimeter, have a b-value ≤ 10.

6. A method for preparing condensed particles according to any one of claims 1 to 5, comprising the following steps: The latex of a vinyl polymer is mixed with a coagulant, and then coagulated and dried to obtain the coagulated particles.

7. The production method according to claim 6, wherein The condensation occurs under neutral conditions.

8. The production method according to claim 6, wherein The coagulation process includes steps of first heat preservation, heating, second heat preservation, and cooling. The temperature of the first heat preservation is 70-80℃, and the time is 1-10 minutes; The heating rate is 3–7 °C / min; The second heat preservation temperature is 90-100℃, and the time is 5-15 minutes; The cooling rate is 0.5–4 °C / min, until the temperature drops to room temperature.

9. A resin composition comprising, by weight, 70-90 parts resin and 10-30 parts impact modifier; wherein The impact modifier includes the condensed particles described in any one of claims 1 to 5.

10. The resin composition according to claim 9, wherein, The resin includes at least one of styrene-acrylonitrile copolymer, polymethyl methacrylate, methyl methacrylate-styrene-acrylonitrile terpolymer, polystyrene, polyvinyl chloride, polycarbonate, polypropylene, polyphenylene ether, polyester, or polyamide; The resin composition has an antibacterial rate of ≥80% and a mildew resistance level of 0-1. The notched impact strength of the resin composition is ≥24 kJ / m. 2 .

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