A conjugated diene-styrene copolymer, preparation method and application thereof, antibacterial polymer material and application thereof

Abstract

The present invention provides a conjugated diene-styrene copolymer, a preparation method and application thereof, an antibacterial polymer material and application thereof, and relates to the field of functional polymer technology. The main skeleton of the conjugated diene-styrene copolymer provided by the present invention is provided by a styrene monomer and / or a diene monomer, and contains quaternary phosphonium salts, quaternary ammonium salts, and sulfonium salt functional groups, and the content of the functional units can be as high as 25 mol%, so that the copolymer has excellent inhibition and killing of bacteria, fungi and viruses, and can be used as an antibacterial agent for preparing antibacterial polymer materials with stable and long-lasting antibacterial properties. As an active ingredient in antibacterial rubber, antibacterial elastomer, antibacterial resin, and antibacterial coating, it can effectively inhibit and kill bacteria, fungi and viruses.

Description

Technical Field

[0001] The present invention relates to the technical field of functional polymers, and in particular to a conjugated diene-styrene copolymer, a preparation method and application thereof, an antibacterial polymer material and application thereof. Background Art

[0002] Antimicrobial and antifungal polymers are a new class of functional materials with bactericidal and antibacterial properties. Their core component is an antimicrobial agent. Adding a very small amount of antimicrobial agent to a polymer material creates an antimicrobial and antifungal polymer. The resulting products also possess hygienic and self-cleaning properties, reducing cross-contamination associated with the use of polymer products. Organic antimicrobial polymers are formed by polymerization or grafting of monomers with antimicrobial functional groups. They are widely available due to their diverse variety, wide range of applications, significant antimicrobial efficacy, and mature application technology, attracting widespread attention. Among them, commercial diene-styrene copolymers include liquid rubber, thermoplastic elastomers, synthetic rubber, and thermoplastic resins. Most are non-polar and can typically be synthesized using anionic polymerization. Diene-styrene monomers can be synthesized into diverse sequence structures through anionic polymerization. Furthermore, the diene microstructure has a wide range of controllable properties, allowing for tailored molecular weight and a narrow molecular weight distribution. Introducing antimicrobial functional groups into diene-styrene copolymers can enhance their antimicrobial properties. However, the antimicrobial activity of existing diene-styrene copolymers is not high enough. Summary of the Invention

[0003] In view of this, the object of the present invention is to provide a conjugated diene-styrene copolymer and its preparation method and application, antibacterial polymer material and its application. The conjugated diene-styrene copolymer provided by the present invention has excellent antibacterial and sterilization properties.

[0004] In order to achieve the above-mentioned object of the invention, the present invention provides the following technical solutions:

[0005] The present invention provides a conjugated diene-styrene copolymer, wherein the structural units include basic units and functional units; the basic units include styrene structural units and / or diene structural units; the molar percentage of the functional units in the conjugated diene-styrene copolymer is 0.1-25%.

[0006] Preferably, the styrene structural unit has a structure shown in formula (1);

[0007] The diene structural unit has one or more structures represented by formula (2) to formula (4);

[0008] The functional unit has one or more structures shown in formula (4) to formula (9);

[0009]

[0010] Wherein, R1 includes -H or C1-C4 alkyl; R2-R4 independently include -H or methyl; R5 includes -H, C1-C16 alkyl, C4-C10 cycloalkyl or C6-C10 aromatic group; R6-R 10 independently include C1-C16 alkyl, C4-C10 cycloalkyl or C6-C10 aromatic groups; X is chlorine, bromine or iodine; the wavy line represents the bond to the main chain;

[0011] The arrangement of the basic units and the functional units includes one or more of a block sequence, a random sequence, an alternating sequence, a tapered sequence and a grafted sequence.

[0012] Preferably, the number average molecular weight of the conjugated diene-styrene copolymer is 1 to 1000 kg / mol, and the molecular weight distribution is 1.02 to 2.

[0013] The present invention also provides a method for preparing the conjugated diene-styrene copolymer described in the above technical solution, comprising the following steps:

[0014] In anhydrous, oxygen-free and protective atmosphere, a basic monomer, a functionalized monomer, a polarity regulator and a first organic solvent are mixed, and alkyl lithium is added to carry out a polymerization reaction to obtain a functionalized copolymer. The basic monomer includes a styrene monomer and / or a diene monomer. The amount of the functionalized monomer accounts for 0.1 to 25% of the total amount of the basic monomer and the functionalized monomer.

[0015] The functionalized copolymer is dissolved in a second organic solvent, and an active halogenated hydrocarbon is added to carry out an ionization reaction to obtain the conjugated diene-styrene copolymer; the halogen in the active halogenated hydrocarbon includes chlorine, bromine or iodine.

[0016] Preferably, the structural formula of the styrene monomer is as follows:

[0017] The structural formula of the diene monomer is as follows:

[0018] The functionalized monomer includes one or more of the following structures:

[0019]

[0020] The polarity regulator includes one or more of potassium alkyl alcohol, tetrahydrofuran, N,N,N',N'-tetramethylethylenediamine, tetrahydrofuran alkyl ether, ditetrahydrofurfuryl propane and N,N-dialkyltetrahydrofurfurylamine;

[0021] The first organic solvent comprises one or more of cyclohexane, cyclopentane, benzene, toluene, hexane, pentane, cyclopentyl methyl ether and tetrahydrofuran;

[0022] The polymerization reaction temperature is 0-100° C., and the reaction time is 0.5-12 hours.

[0023] Preferably, the second organic solvent comprises one or more of toluene, cyclopentyl methyl ether, tetrahydrofuran, methanol, ethanol, dimethyl sulfoxide, N,N-dimethylformamide, dichloromethane and chloroform;

[0024] The active halogenated hydrocarbon includes a halogenated alkyl compound or a halogenated aryl compound;

[0025] The molar ratio of the functionalized monomer to the active halogenated hydrocarbon is 1:0.8-1.5;

[0026] The temperature of the ionization reaction is 25 to 150° C., and the time is 0.5 to 12 hours.

[0027] The present invention also provides an antibacterial polymer material, comprising a conjugated diene-styrene copolymer and a polymer material, wherein the conjugated diene-styrene copolymer is the conjugated diene-styrene copolymer described in the above technical solution or the conjugated diene-styrene copolymer prepared by the preparation method described in the above technical solution.

[0028] Preferably, the mass ratio of the conjugated diene-styrene copolymer to the polymer material is 1 to 10:100.

[0029] Preferably, the polymer material includes one or more of plastic, rubber and fiber.

[0030] The present invention also provides the use of the conjugated diene-styrene copolymer described in the above technical solution, the conjugated diene-styrene copolymer prepared by the preparation method described in the above technical solution, or the antibacterial polymer material described in the above technical solution in the preparation of antibacterial agents or antiviral agents.

[0031] The main skeleton of the conjugated diene-styrene copolymer provided by the present invention is provided by styrene monomers and / or diene monomers, and contains quaternary phosphonium salts, quaternary ammonium salts, and sulfonium salt functional groups, and the content of the functional units can be as high as 25 mol%. This makes the copolymer have excellent performance in inhibiting and killing bacteria, fungi, and viruses, and can be used as an antibacterial agent to prepare antibacterial polymer materials with stable and long-lasting antibacterial properties. As an active ingredient in antibacterial rubbers, antibacterial elastomers, antibacterial resins, and antibacterial coatings, it can effectively inhibit and kill bacteria, fungi, and viruses.

[0032] The present invention also provides a method for preparing the conjugated diene-styrene copolymer described in the above technical solution. The present invention prepares the conjugated diene-styrene copolymer through an anionic copolymerization method and a post-functionalization modification method. The degree of ionization of the copolymer can be controlled, imparting special antibacterial properties to the material. The resulting conjugated diene-styrene copolymer can contain functional units up to 25 mol%. This method addresses the problem of low functional group content and limited degree of ionization in conjugated diene-styrene copolymers prepared by existing preparation methods, which in turn limits their application areas. Furthermore, the preparation method provided by the present invention is simple in process, easy to operate, low in cost, and suitable for industrial production.

[0033] The conjugated diene-styrene copolymer provided by the present invention is used to prepare an antibacterial polymer material, which has no migration and release of antibacterial agents and can maintain high-efficiency, stable, low-toxic, safe and long-lasting antibacterial and antimicrobial effects. DETAILED DESCRIPTION

[0034] The present invention provides a conjugated diene-styrene copolymer, wherein the structural units include basic units and functional units; the basic units include styrene structural units and / or diene structural units; the molar percentage of the functional units in the conjugated diene-styrene copolymer is 0.1-25%.

[0035] In the present invention, the styrene structural unit preferably has a structure represented by formula (1); the diene structural unit preferably has a structure represented by formula (2) and / or formula (3); the functional unit preferably has one or more structures represented by formula (4) to formula (9);

[0036]

[0037] Wherein, R1 includes -H or C1-C4 alkyl; R2-R4 independently include -H or methyl; R5 includes -H, C1-C16 alkyl, C4-C10 cycloalkyl or C6-C10 aromatic group; R6-R 10 Independently include C1~C16 alkyl, C4~C10 cycloalkyl or C6~C10 aromatic group; X is chlorine, bromine or iodine; the wavy line represents the connection bond to the main chain.

[0038] In the present invention, the C1-C4 alkyl group preferably includes methyl, ethyl, C3 alkyl, or C4 alkyl; the C3 alkyl group preferably includes n-propyl or isopropyl; the C4 alkyl group preferably includes n-butyl, isobutyl, or tert-butyl. In the present invention, the substitution position of R1 includes the ortho, meta, or para position.

[0039] In the present invention, the C1~C16 alkyl group preferably includes a C1~C16 straight-chain alkyl group or a C1~C16 branched-chain alkyl group; the C1~C16 alkyl group preferably includes a methyl group, an ethyl group, a C3~C16 alkyl group; the C3~C16 alkyl group preferably includes a C3 alkyl group, a C4 alkyl group, a C5 alkyl group, a C6 alkyl group, a C7 alkyl group, a C8 alkyl group, a C9 alkyl group, a C10 alkyl group, a C11 alkyl group, a C12 alkyl group, a C13 alkyl group, a C14 alkyl group, a C15 alkyl group or a C16 alkyl group.

[0040] In the present invention, the C4-C10 cycloalkyl group preferably includes a C3 cycloalkyl group, a C4 cycloalkyl group, a C5 cycloalkyl group, a C6 cycloalkyl group, a C7 cycloalkyl group, a C8 cycloalkyl group, a C9 cycloalkyl group or a C10 cycloalkyl group.

[0041] In the present invention, the C6-C10 aromatic group preferably includes phenyl, C7 aromatic, C8 aromatic, C9 aromatic or C10 aromatic; the C7 aromatic group preferably includes methylstyrene, and the substitution site of the methyl group in the methylstyrene preferably includes ortho, meta or para; the C8 aromatic group preferably includes ethylstyrene and dimethylstyrene, and the substitution site of the ethyl group in the ethylstyrene preferably includes ortho, meta or para, and the substitution site of the methyl group in the dimethylstyrene preferably includes ortho, meta or para; the C9 aromatic group preferably includes propylstyrene or methyl-ethylstyrene; the substitution site of the propyl group in the propylstyrene preferably includes ortho, meta or para. Preferably, the propyl group includes ortho, meta or para positions, and the propyl group includes n-propyl or isopropyl; the substitution sites of the methyl and ethyl groups in the methyl-ethylstyrene preferably include ortho, meta or para positions; the C10 aromatic group preferably includes butylstyrene, methyl-propylstyrene or diethylstyrene; the substitution site of the butyl group in the butylstyrene preferably includes ortho, meta or para positions, and the butyl group preferably includes n-butyl, isobutyl or tert-butylisothiazolyl; the substitution sites of the methyl and propyl groups in the methyl-propylstyrene preferably include ortho, meta or para positions, and the propyl group preferably includes n-propyl or isopropyl; the substitution site of the ethyl group in the diethylstyrene preferably includes ortho, meta or para positions.

[0042] In the present invention, the molar percentage of the functional units in the conjugated diene-styrene copolymer is 0.1-25%, more preferably 2-20%, and in specific embodiments can be 0.1%, 0.5%, 1%, 2%, 3%, 4%, 5%, 5.2%, 6%, 7%, 8%, 9%, 9.5%, 9.6%, 9.7%, 9.9%, 10%, 10.1%, 10.2%, 10.5%, 11%, 12%, 13%, 14%, 15%, 16%, 17%, 8%, 19%, 20%, 20.5%, 21%, 22%, 23%, 24% or 25%. In the present invention, in the conjugated diene-styrene copolymer, the molar percentage of the styrene structural unit is preferably 0 to 99.9%, the molar percentage of the diene structural unit is preferably 0 to 99.9%, and the total molar percentage of the styrene structural unit and the diene structural unit is preferably 75 to 99.9%. In the present invention, the mole percentage of styrene structural units in the conjugated diene-styrene copolymer is preferably 0-99.9%, more preferably 15-65%. In the present invention, the mole percentage of styrene structural units in the conjugated diene-styrene copolymer is preferably 15-65%. In specific embodiments, it can be 15%, 16%, 17%, 18%, 19%, 19.5%, 19.6%, 19.8%, 20%, 20.3%, 20.5%, 25%, 30%, 30.1%, 35%, 40%, 45%, 50%, 55%, 55.1%, 60%, 61.5% or 65%.

[0043] In the present invention, the arrangement of the basic units and functional units preferably includes one or more of a block sequence, a random sequence, an alternating sequence, a tapered sequence and a grafted sequence.

[0044] In the present invention, the number average molecular weight of the conjugated diene-styrene copolymer is preferably 1 to 1000 kg / mol, and the molecular weight distribution is preferably 1.02 to 2.

[0045] The main skeleton of the conjugated diene-styrene copolymer provided by the present invention is provided by styrene monomers and / or diene monomers, and contains quaternary phosphonium salts, quaternary ammonium salts, and sulfonium salt functional groups, and the content of the functional units can be as high as 25 mol%. This makes the copolymer have excellent antibacterial and sterilization properties, and can be used as an antibacterial agent to prepare antibacterial polymer materials with stable and long-lasting antibacterial properties. As an active ingredient in antibacterial rubber, antibacterial elastomer, antibacterial resin or antibacterial coating, it can effectively inhibit and kill bacteria, fungi and viruses.

[0046] The present invention provides a method for preparing the conjugated diene-styrene copolymer described in the above technical solution, comprising the following steps:

[0047] In anhydrous, oxygen-free and protective atmosphere, a base monomer, a functionalized monomer, a polarity modifier and a first organic solvent are mixed, and alkyl lithium is added to carry out a polymerization reaction to obtain a functionalized copolymer; the base monomer comprises a styrene monomer and / or a diene monomer; and the amount of the functionalized monomer accounts for 0.1 to 25% of the total amount of the base monomer and the functionalized monomer;

[0048] The functionalized copolymer is dissolved in a second organic solvent, and active halogenated hydrocarbon is added to carry out ionization reaction to obtain the conjugated diene-styrene copolymer.

[0049] Unless otherwise specified, the materials and equipment used in the present invention are all commercially available products in the art.

[0050] The present invention mixes a basic monomer, a functionalized monomer, a polarity regulator and a first organic solvent in an anhydrous, oxygen-free and protective atmosphere, and adds alkyl lithium to carry out polymerization reaction to obtain a functionalized copolymer. The basic monomer includes a styrene monomer and / or a diene monomer. The amount of the functionalized monomer accounts for 0.1 to 25% of the total amount of the basic monomer and the functionalized monomer.

[0051] In the present invention, the water content of the anhydrous material is preferably less than 5 ppm (ie, 0.0005 wt%), and the oxygen content of the anaerobic material is preferably less than 5 ppm.

[0052] In the present invention, the protective atmosphere preferably includes nitrogen, argon or helium.

[0053] In the present invention, the molar ratio of the styrene monomer, diene monomer and functional monomer is based on the molar percentage of the styrene structural unit, diene structural unit and functional unit in the conjugated diene-styrene copolymer.

[0054] In the present invention, the structural formula of the styrene monomer is as follows: The definition of R1 is the same as that of R1 in formula (1).

[0055] In the present invention, the structural formula of the diene monomer is as follows: The definitions of R2 to R4 are the same as those of R2 to R4 in the above formulae (2) to (4).

[0056] In the present invention, the functionalized monomer preferably includes one or more of the following structures:

[0057]

[0058] Among them, R6~R 10 The definition of R6 to R in formula (5) to (10) is the same as that of 10The definition is the same.

[0059] In the present invention, the functionalized monomer preferably comprises one or more of formulas VB-1 to VB-14:

[0060]

[0061] In the present invention, the polarity modifier preferably includes one or more of potassium alkyl alkoxide, tetrahydrofuran, N,N,N',N'-tetramethylethylenediamine, tetrahydrofuran alkyl ether, ditetrahydrofurfuryl propane, and N,N-dialkyltetrahydrofurfurylamine; the potassium alkyl alkoxide preferably includes potassium tert-butoxide and / or potassium tert-amyl alkoxide. In the present invention, the molar ratio of the polarity modifier to the functionalized monomer is preferably 0 to 100:1, and in specific embodiments, it can be 0:1, 5:1, 10:1, 20:1, 30:1, 40:1, 50:1, 60:1, 70:1, 80:1, 90:1, or 100:1.

[0062] In the present invention, the first organic solvent preferably includes one or more of cyclohexane, cyclopentane, benzene, toluene, hexane, pentane, cyclopentyl methyl ether and tetrahydrofuran, and more preferably cyclohexane, cyclopentane, toluene or cyclopentyl methyl ether. In the present invention, the solid-liquid ratio of the functionalized monomer to the first organic solvent is preferably 1g:25-500mL, and in specific embodiments, it can be 1g:25mL, 1g:50mL, 1g:100mL, 1g:150mL, 1g:200mL, 1g:250mL, 1g:300mL, 1g:350mL, 1g:400mL, 1g:450mL or 1g:500mL.

[0063] In the present invention, the alkyl lithium preferably includes at least one of alkyl monolithium, alkyl dilithium, and alkyl polylithium, and more preferably includes one or more of butyl lithium, pentyl lithium, hexyl lithium, 1,6-dilithium hexane, naphthalene lithium, 1,1,4,4-tetraphenylbutyl lithium, 1,3-diisopropyl dilithium, and divinylbenzene coupled polylithium. In the present invention, the molar ratio of the functionalized monomer to the alkyl lithium is preferably 1:0.0001 to 100, and in specific embodiments, it can be 1:0.0001, 1:0.001, 1:0.01, 1:0.1, 1:1, 1:5, 1:10, 1:20, 1:30, 1:40, 1:50, 1:60, 1:70, 1:80, 1:90, or 1:100.

[0064] In the present invention, the temperature of the polymerization reaction is preferably 0-100°C, and in specific embodiments it can be 0°C, 10°C, 20°C, 25°C, 30°C, 40°C, 50°C, 60°C, 70°C, 80°C, 90°C or 100°C; the time of the polymerization reaction is preferably 0.5-12h, and in specific embodiments it can be 0.5h, 1h, 2h, 3h, 4h, 5h, 6h, 7h, 8h, 9h, 10h, 11h or 12h.

[0065] In the present invention, the polymerization reaction can also be a three-stage polymerization reaction, which preferably includes a first-stage polymerization reaction, a second-stage polymerization reaction, and a third-stage polymerization reaction. Specifically, in an anhydrous, oxygen-free, and protective atmosphere, a polarity modifier, a first organic solvent, and an alkyl lithium are mixed, a portion of the styrene monomer is added to carry out a first-stage polymerization reaction, then a diene monomer and a functionalized monomer are added to carry out a second-stage polymerization reaction, and then the remaining styrene monomer is added to carry out a third-stage polymerization reaction. In the present invention, the mass of the portion of the styrene monomer accounts for 0 to 99% of the total mass of the styrene monomer, and in specific embodiments, it can be 0%, 10%, 20%, 30%, 40%, 50%, 60%, 70%, 80%, 90%, or 99%. In the present invention, the temperature of the polymerization reaction is preferably 0 to 100°C, and in specific embodiments, it can be 0°C, 10°C, 20°C, 30°C, 40°C, 50°C, 60, 65°C, 70°C, 80°C, 90°C or 100°C; the time of the polymerization reaction is preferably 10 min to 4 h, and in specific embodiments, it can be 10 min, 15 min, 0.5 h, 0.75 h, 1 h, 1.5 h, 2 h, 2.5 h, 3 h, 3.5 h or 4 h. In the present invention, the temperature of the second-stage polymerization reaction is 0 to 100°C, and in specific embodiments can be 0°C, 10°C, 20°C, 30°C, 40°C, 50°C, 55°C, 60, 65°C, 70°C, 80°C, 85°C, 90°C or 100°C; the time of the second-stage polymerization reaction is preferably 10 min to 4 h, and in specific embodiments can be 10 min, 15 min, 0.5 h, 0.75 h, 1 h, 1.5 h, 2 h, 2.5 h, 3 h, 3.5 h or 4 h. In the present invention, the temperature of the three-stage polymerization reaction is preferably 0-100°C, and in specific embodiments it can be 0°C, 10°C, 20°C, 30°C, 40°C, 50°C, 60, 65°C, 70°C, 80°C, 90°C or 100°C; the time of the three-stage polymerization reaction is preferably 10 min to 4 h, and in specific embodiments it can be 10 min, 15 min, 0.5 h, 0.75 h, 1 h, 1.5 h, 2 h, 2.5 h, 3 h, 3.5 h or 4 h.

[0066] After completing the polymerization reaction, the present invention preferably further comprises: adding a hydrochloric acid methanol solution to terminate the reaction, then adding an antioxidant and ethanol to precipitate a copolymer glue, washing the copolymer glue with acidic water and ethanol in sequence until neutral, and drying to obtain a functionalized copolymer glue. In the present invention, the concentration of hydrochloric acid in the hydrochloric acid methanol solution is preferably 0.1 to 5 mol / L, and in specific embodiments can be 0.1 mol / L, 0.5 mol / L, 1 mol / L, 1.5 mol / L, 2 mol / L, 2.5 mol / L, 3 mol / L, 3.5 mol / L, 4 mol / L, 4.5 mol / L or 5 mol / L. In the present invention, the antioxidant preferably includes one or more of 2,6-di-tert-butyl-4-methylphenol, 4,4'-butylenebis(6-tert-butyl-3-methylphenol), dilauryl thiodipropionate, and tris(2,4-di-tert-butylphenyl) phosphite; the antioxidant is preferably used in the form of an antioxidant solution, and the solvent in the antioxidant solution preferably includes ethanol; the concentration of the antioxidant solution is preferably 0.01 to 1.0 mol / L. In the present invention, the molar ratio of the functionalized monomer to the antioxidant is preferably 1:0.01 to 100. In specific embodiments, it can be 1:0.01, 1:0.05, 1:0.1, 1:1, 1:5, 1:10, 1:20, 1:30, 1:40, 1:50, 1:60, 1:70, 1:80, 1:90, or 1:100. In the present invention, the pH value of the acidic water is preferably 5.0 to 6.9, and in specific embodiments, it can be 5.0, 5.5, 6, 6.5, or 6.9. The acidic water is preferably obtained by adjusting the pH value of water with an acid, and the acid preferably includes a biomass acid, more preferably citric acid and / or malic acid. In the present invention, the drying preferably includes vacuum drying, and the drying temperature is preferably 20 to 60°C, and in specific embodiments, it can be 20°C, 30°C, 40°C, 50°C, or 60°C. The present invention does not specifically limit the drying time, and drying to constant weight is sufficient.

[0067] After obtaining the functionalized copolymer, the present invention dissolves the functionalized copolymer in a second organic solvent, adds active halogenated hydrocarbons to carry out ionization reaction, and obtains the conjugated diene-styrene copolymer; the halogen in the active halogenated hydrocarbons includes chlorine, bromine or iodine.

[0068] In the present invention, the second organic solvent preferably includes one or more of toluene, cyclopentyl methyl ether, tetrahydrofuran, methanol, ethanol, dimethyl sulfoxide, N,N-dimethylformamide, dichloromethane, and chloroform, and more preferably toluene, tetrahydrofuran, ethanol, dimethyl sulfoxide, dichloromethane, or chloroform. In the present invention, the solid-to-liquid ratio of the functionalized copolymer glue to the second organic solvent is preferably 1g:25-500mL, and in specific embodiments, it can be 1g:25mL, 1g:50mL, 1g:100mL, 1g:200mL, 1g:300mL, 1g:400mL, or 1g:500mL.

[0069] In the present invention, the active halogenated hydrocarbon preferably includes a halogenated alkyl compound or a halogenated aryl compound; the halogenated alkyl compound preferably includes alkyl chloride, alkyl bromide or alkyl iodide; the halogenated aryl compound preferably includes aryl chloride, aryl bromide or aryl iodide; the alkyl group in the halogenated alkyl compound preferably includes methyl, ethyl, propyl, butyl, pentyl, dodecyl or octadecyl; the aryl group in the halogenated aryl compound preferably includes phenyl, methylphenyl, ethylphenyl, propylphenyl, butylphenyl or naphthylphenyl.

[0070] In the present invention, the molar ratio of the functionalized monomer to the active halogenated hydrocarbon is preferably 1:0.8-1.5, more preferably 1:0.9-1.2, and in specific embodiments can be 1:0.8, 1:0.9, 1:1, 1:1.1, 1:1.2, 1:1.3, 1:1.4 or 1:5.

[0071] In the present invention, the temperature of the ionization reaction is preferably 25 to 150° C., and in specific embodiments, it can be 25° C., 30° C., 40° C., 50° C., 60° C., 70° C., 80° C., 90° C., 100° C., 110° C., 120° C., 130° C., 140° C., or 150° C.; the time of the ionization reaction is preferably 0.5 to 12 hours, and in specific embodiments, it can be 0.5 hours, 1 hour, 2 hours, 3 hours, 4 hours, 5 hours, 6 hours, 7 hours, 8 hours, 9 hours, 10 hours, 11 hours, or 12 hours. In the present invention, after the ionization reaction reaches a certain level, solid insoluble matter is precipitated from the second organic solvent.

[0072] After the ionization reaction is completed, the present invention preferably further comprises: filtering the resulting ionization reaction solution, washing the resulting solid component with cyclohexane 2-3 times, and then drying to obtain a conjugated diene-styrene copolymer. In the present invention, the drying temperature is preferably 30-100°C, and in specific embodiments, it can be 30°C, 40°C, 50°C, 60°C, 70°C, 80°C, 90°C, or 100°C. The present invention does not specifically limit the drying time, and drying to constant weight is sufficient.

[0073] The present invention prepares conjugated diene-styrene copolymers through an anionic copolymerization method and a post-functionalization modification method. The degree of ionization of the copolymer can be controlled, imparting special antibacterial properties to the material. The content of functional units in the prepared conjugated diene-styrene copolymer can be as high as 25 mol%. This solves the problem of low functional group content and limited degree of ionization in conjugated diene-styrene copolymers prepared by existing preparation methods, which in turn limits their application areas. Furthermore, the preparation method provided by the present invention is simple in process, easy to operate, low in cost, and suitable for industrial production.

[0074] The present invention also provides an antibacterial polymer material, comprising a conjugated diene-styrene copolymer and a polymer material, wherein the conjugated diene-styrene copolymer is the conjugated diene-styrene copolymer described in the above technical solution or the conjugated diene-styrene copolymer prepared by the preparation method described in the above technical solution.

[0075] In the present invention, the mass ratio of the conjugated diene-styrene copolymer to the polymer material is preferably 1 to 10:100, more preferably 2 to 8:100. In specific embodiments, it can be 1:100, 1.5:100, 2:100, 2.5:100, 3:100, 3.5:100, 4:100, 4.5:100, 5:100, 5.5:100, 6:100, 6.5:100, 7:100, 7.5:100, 8:100, 8.5:100, 9:100, 9.5:100 or 10:100.

[0076] In the present invention, the polymer material preferably includes one or more of plastic, rubber and fiber; the plastic preferably includes one or more of polyethylene, polypropylene, polystyrene, styrene-butadiene resin, polyvinyl chloride, polyester and polyphenylene ether; the rubber preferably includes one or more of polybutadiene, polyisoprene, polymyrcene, butyl rubber, butadiene-pentadiene rubber, styrene-butadiene rubber and nitrile rubber; the fiber preferably includes one or more of polypropylene, chloroprene, vinylon and polyester.

[0077] The conjugated diene-styrene copolymer provided by the present invention is used to prepare an antibacterial polymer material, which has no migration and release of antibacterial agents and can maintain high-efficiency, stable, low-toxic, safe and long-lasting antibacterial and antimicrobial effects.

[0078] The present invention provides the use of the conjugated diene-styrene copolymer described in the above technical solution, the conjugated diene-styrene copolymer prepared by the preparation method described in the above technical solution, or the antibacterial polymer material described in the above technical solution in the preparation of antibacterial or antiviral agents. In the present invention, the conjugated diene-styrene copolymer and the antibacterial polymer material are preferably used as antibacterial agents or raw materials for the preparation of antibacterial agents; the antibacterial agent preferably includes antibacterial rubber, antibacterial elastomer, antibacterial resin or antibacterial coating; the antibacterial agent is preferably an antifungal agent and / or an antibacterial agent. In the present invention, the conjugated diene-styrene copolymer and the antibacterial polymer material are preferably used as raw materials for the preparation of antiviral agents; the antiviral agent preferably includes antiviral rubber, antiviral elastomer, antiviral resin or antiviral coating.

[0079] To further illustrate the present invention, the conjugated diene-styrene copolymer provided by the present invention, its preparation method and application, antibacterial polymer material and its application are described in detail below with reference to the examples, but they should not be construed as limiting the scope of protection of the present invention.

[0080] Example 1

[0081] Preparation of quaternary ammonium antibacterial conjugated butadiene-styrene copolymer (denoted as SB-N1-Cl)

[0082] A water- and oxygen-free reactor was filled with high-purity nitrogen. 2500 mL of cyclohexane, 5 mL of 0.5 M potassium tert-amyl alcohol, and 10 mL of 0.5 M n-butyl lithium initiator were added sequentially. The mixture was stirred at room temperature for 5 minutes. Then, 375 g of butadiene, 100 g of styrene, and 25 g of VB-1 amine functional monomer were added all at once. Polymerization was carried out at 50-60°C for 2 hours. The reaction was terminated by adding 2 mL of 1 M methanolic hydrochloric acid to obtain an amine-functionalized styrene-butadiene rubber solution. The solution was then poured into 2.5 L of ethanol containing 50 mL of an antioxidant to precipitate the copolymer. The solution was washed with acidic deionized water (adjusted to pH 6.5 with citric acid) and ethanol until neutral, and dried in a vacuum oven at 40°C to constant weight to obtain the functionalized copolymer with a yield of 100%. The functionalized copolymer contained 87 mol% of polybutadiene 1,4-structures, 19.8 mol% of styrene structures, and 5.2 mol% of VB-1 amine functional structures. The number average molecular weight of the functionalized copolymer is 125600 g / mol, and the molecular weight distribution is 1.02. The antioxidant is an ethanol solution of 2,6-di-tert-butyl-4-methylphenol with a mass fraction of 0.5%.

[0083] 100 g of the functionalized copolymer was dissolved in toluene, and 3.9 g of benzyl chloride was added at 60°C for quaternization for 4 hours. The resulting solid was filtered, washed two to three times with cyclohexane, and dried at 60°C to constant weight. This yielded a quaternary antibacterial conjugated butadiene-styrene copolymer (SB-N1-Cl) with a yield of 103.6%. The degree of quaternization was 95%, the number average molecular weight was 123,700 g / mol, and the molecular weight distribution was 1.08.

[0084] Example 2

[0085] Preparation of quaternary ammonium antibacterial conjugated isoprene-methylstyrene copolymer (denoted as MSI-N3-Br)

[0086] An anhydrous and oxygen-free reactor was filled with high-purity nitrogen, and 2500 mL of cyclopentane, 4 mL of 0.5 M TMEDA regulator, and 10 mL of 0.5 M tert-butyl lithium initiator were added in sequence. The mixture was stirred at room temperature for 5 minutes, and then 350 g of isoprene, 100 g of methylstyrene, and 50 g of VB-3 amine functional monomer were added. The polymerization reaction was carried out at 50-60° C. for 2 hours. 2 mL of 1 M hydrochloric acid methanol solution was added to terminate the reaction to obtain amine-functionalized isoprene-methylstyrene glue. The solution was poured into 2.5 L of ethanol containing 50 mL of an antioxidant to precipitate a copolymer glue. The solution was repeatedly washed with acidic deionized water (adjusted to pH 6.2 with tartaric acid) and ethanol until neutral, and dried in a vacuum drying oven at 45° C. to constant weight to obtain a functionalized copolymer glue with a yield of 100%. The functionalized copolymer contains 20.5 mol% methylstyrene structures, 10.2 mol% VB-3 amine functional structures, and the remainder is polyisoprene structures. The polyisoprene structures contain 57 mol% polyisoprene 3,4-structures, 40 mol% polyisoprene 1,4-structures, and 3 mol% polyisoprene 1,2-structures. The functionalized copolymer has a number-average molecular weight of 135,400 g / mol and a molecular weight distribution of 1.06. The antioxidant is a 0.5% (mass fraction) ethanol solution of 2,6-di-tert-butyl-4-methylphenol.

[0087] 100 g of functionalized copolymer glue was dissolved in cyclopentyl methyl ether, 3.0 g of ethyl bromide was added at 80°C for quaternization reaction for 5 h, filtered, and the resulting solid component was washed with cyclohexane 2 to 3 times and dried at 80°C to constant weight to obtain a quaternary antibacterial conjugated isoprene-methylstyrene copolymer (denoted as MSI-N3-Br) with a yield of 102.7%, a degree of quaternization of 96%, a number average molecular weight of 139700 g / mol, and a molecular weight distribution of 1.16.

[0088] Example 3

[0089] Preparation of quaternary ammonium antibacterial conjugated isoprene-styrene copolymer (denoted as SP-N5-I)

[0090] A water-free, oxygen-free reactor was filled with high-purity nitrogen. 2500 mL of pentane, 1 mL of 0.5 M THF, and 10 mL of 0.5 M n-butyl lithium initiator were added sequentially. The mixture was stirred at room temperature for 3 minutes. Then, 180 g of piperylene, 270 g of styrene, and 50 g of VB-5 amine functional monomer were added all at once. The mixture was reacted at 55-60°C for 2 hours. The reaction was terminated by adding 2 mL of 1 M methanolic hydrochloric acid. The amine-functionalized piperylene-styrene glue was poured into 2.5 L of ethanol containing 50 mL of an antioxidant to precipitate the copolymer. The mixture was then washed repeatedly with acidic deionized water (adjusted to pH 6.3 with malic acid) and ethanol until neutral. The mixture was dried in a vacuum drying oven at 40°C to constant weight to obtain the functionalized copolymer with a yield of 100%. The functionalized copolymer contains 55.1 mol% styrene structures, 9.7 mol% VB-5 amine functional structures, and the remainder is polyisoprene structures. The polyisoprene structure contains 91 mol% polyisoprene 1,4-units and 9 mol% polyisoprene 1,2-units. The functionalized copolymer has a molecular weight of 105,900 g / mol and a molecular weight distribution of 1.04. The antioxidant is a 0.5% (mass fraction) ethanol solution of 2,6-di-tert-butyl-4-methylphenol.

[0091] 100 g of functionalized copolymer glue was dissolved in tetrahydrofuran, 3.2 g of iodomethane was added at 70°C for quaternization reaction for 3 hours, filtered, and the resulting solid component was washed with cyclohexane 2 to 3 times and dried at 50°C to constant weight to obtain a quaternary antibacterial conjugated isoprene-styrene copolymer (denoted as SP-N5-I) with a yield of 102.9%, a degree of quaternization of 92%, a number average molecular weight of 113400 g / mol, and a molecular weight distribution of 1.11.

[0092] Example 4

[0093] Preparation of quaternary ammonium antibacterial conjugated S(BN)S copolymer (denoted as SBS-N7-Cl)

[0094] A water-free, oxygen-free reactor was filled with high-purity nitrogen. 2500 mL of hexane, 2 mL of 0.5 M THF, and 10 mL of 0.5 M sec-butyl lithium initiator were added sequentially. The mixture was stirred at room temperature for 3 minutes. First, 75 g of styrene was added, and a first-stage polymerization reaction was carried out at 60-65°C for 0.5 h. Then, 300 g of butadiene and 50 g of VB-7 monomer were added, and a second-stage polymerization reaction was carried out at 60-65°C for 0.5 h. Finally, 75 g of styrene was added, and a third-stage polymerization reaction was continued at 60-65°C for 0.5 h. Finally, 3 mL of 1 M methanolic hydrochloric acid was added to terminate the reaction. The amine-functionalized S(BN)S copolymer was poured into 2.5 L of ethanol containing 50 mL of an antioxidant to precipitate the copolymer. The product was then washed repeatedly with acidic deionized water (adjusted to pH 6.5 with citric acid) and ethanol until neutral, and dried in a vacuum oven at 45°C to constant weight to obtain a functionalized copolymer with a yield of 100%. The copolymer contained 30.1 mol% styrene structures, 9.9 mol% VB-7 amine functional structures, and the remainder was polybutadiene. The polybutadiene structure contained 80 mol% 1,4-unit polybutadiene and 20 mol% 1,2-unit polybutadiene. The number-average molecular weight of the functionalized copolymer was 101,600 g / mol, with a molecular weight distribution of 1.05. The antioxidant was a 0.5% (mass fraction) ethanol solution of 2,6-di-tert-butyl-4-methylphenol.

[0095] 100 g of functionalized copolymer glue was dissolved in toluene, 3.4 g of bromobutane was added at 70°C for quaternization reaction for 5 h, filtered, and the resulting solid component was washed with cyclohexane 2 to 3 times and dried at 80°C to constant weight to obtain a quaternary antibacterial conjugated S(BN)S copolymer (denoted as SBS-N7-Cl) with a yield of 103.0%, a degree of quaternization of 89%, a number average molecular weight of 108500 g / mol, and a molecular weight distribution of 1.10.

[0096] Example 5

[0097] Preparation of quaternary ammonium antibacterial conjugated S(IS')S copolymer (denoted as SIS-S8-I)

[0098] In an anhydrous and oxygen-free reactor, high-purity nitrogen was filled, and 2500 mL of cyclohexane, 0.1 mL of 0.5 M ditetrahydrofurfuryl propane regulator, and 10 mL of 0.5 M sec-butyl lithium initiator were added in sequence. The mixture was stirred at room temperature for 5 min, and then 50 g of styrene was added. The first stage polymerization reaction was carried out at 60-65 ° C for 0.5 h. Then, 350 g of isoprene and 50 g of VB-8 monomer were added. The second stage polymerization reaction was carried out at 50-55 ° C for 0.75 h. Then, styrene was added. The sulfide-functionalized S(IS')S copolymer was prepared by adding 50 g of olefins and continuing the polymerization at 60-65°C for 0.5 h in three stages. The reaction was terminated by adding 2 mL of 1 M methanolic hydrochloric acid solution to obtain a thioether-functionalized S(IS')S copolymer. The copolymer was then poured into 2.5 L of ethanol containing 50 mL of an antioxidant to precipitate the copolymer. The copolymer was then washed repeatedly with acidic deionized water (adjusted to pH 6.5 with citric acid) and ethanol until neutral. The copolymer was then dried in a vacuum oven at 50°C to constant weight to obtain a functionalized copolymer with a yield of 100%. The functionalized copolymer contained 19.6 mol% styrene structures, 9.7 mol% VB-8 thioether functional structures, and the remainder was polyisoprene structures. The polyisoprene structure contained 65 mol% polyisoprene 1,4-structures and 35 mol% polyisoprene 3,4-structures. The number average molecular weight of the functionalized copolymer was 135,500 g / mol, with a molecular weight distribution of 1.08. The antioxidant is an ethanol solution of 2,6-di-tert-butyl-4-methylphenol with a mass fraction of 0.5%.

[0099] 100 g of functionalized copolymer was dissolved in toluene, 3.4 g of ethyl bromide was added at 70°C for sulfonation reaction for 5 h, and the resulting solid component was filtered. The solid component was washed 2 to 3 times with cyclohexane and dried at 70°C to constant weight to obtain a quaternary ammonium antibacterial conjugated S(IS')S copolymer (denoted as SIS-S8-I) with a yield of 102.9%, a degree of sulfonation of 88%, a number average molecular weight of 140200 g / mol, and a molecular weight distribution of 1.15.

[0100] Example 6

[0101] Preparation of quaternary phosphine-type antibacterial conjugated S(PP')S copolymer (denoted as S-P11-SI)

[0102] High-purity nitrogen was filled into an anhydrous and oxygen-free reactor, and 2500 mL of cyclohexane, 5 mL of 0.5 M N, N-dimethyltetrahydrofurfurylamine regulator and 10 mL of 0.5 M sec-butyl lithium initiator were added in sequence. The mixture was stirred at room temperature for 5 min, and then 50 g of styrene was added first, and the reaction was carried out at 60-65° C. for 0.5 h. Subsequently, 350 g of isopentadiene and 50 g of VB-11 monomer were added, and the second-stage polymerization reaction was carried out at 80-85° C. for 1 h. Then, 50 g of styrene was added, and the third-stage polymerization reaction was continued at 60-65° C. for 0.5 h. Finally, 2.5 mL of 1 M hydrochloric acid methanol solution was added to terminate the reaction to obtain a phosphine-functionalized S(PP')S copolymer glue solution, which was poured into 2.5 L of ethanol containing 50 mL of an antioxidant to precipitate the copolymer glue. The product was then washed repeatedly with acidic deionized water (adjusted to pH 6.0 with tartaric acid) and ethanol until neutral, and dried in a vacuum oven at 40°C to constant weight to obtain a functionalized copolymer with a yield of 99%. The copolymer contained 19.5 mol% styrene structures, 9.6 mol% VB-11 phosphine-containing functional structures, and the remainder was polyisoprene structures. The polyisoprene structures contained 69 mol% polyisoprene 1,4 structures and 31 mol% polyisoprene 1,2 structures. The number-average molecular weight of the functionalized copolymer was 123,500 g / mol, with a molecular weight distribution of 1.11. The antioxidant was a 0.5% (mass fraction) ethanol solution of 2,6-di-tert-butyl-4-methylphenol.

[0103] 100 g of functionalized copolymer glue was dissolved in cyclopentyl methyl ether, 2.4 g of iodomethane was added at 80°C for quaternary phosphination reaction for 6 hours, filtered, and the resulting solid component was washed with cyclohexane 2 to 3 times and dried at 80°C to constant weight to obtain a quaternary phosphine-type antibacterial conjugated S(PP')S copolymer (denoted as S-P11-SI) with a yield of 102.3%, a degree of quaternization of 98%, a number average molecular weight of 130,800 g / mol, and a molecular weight distribution of 1.18.

[0104] Example 7

[0105] Preparation of Sulfonium Antibacterial Conjugated Isoprene-4-tert-Butylstyrene Copolymer (TBS-IP-VB12-I)

[0106] An anhydrous and oxygen-free reactor was filled with high-purity nitrogen, and 2500 mL of cyclopentane, 5 mL of 0.5 M potassium tert-butoxide regulator, and 10 mL of 0.5 M tert-butyl lithium initiator were added in sequence. The mixture was stirred at room temperature for 5 minutes, and then 100 g of isoprene, 350 g of p-tert-butylstyrene, and 50 g of VB-12 thioether functional structural unit were added all at once. The mixture was reacted at 50-65° C. for 2 hours. 2.5 mL of 1 M methanolic hydrochloric acid solution was added to terminate the reaction to obtain a thioether-functionalized isoprene-p-tert-butylstyrene glue solution. The solution was poured into 2.5 L of ethanol containing 50 mL of an antioxidant to precipitate a copolymer. The solution was washed repeatedly with acidic deionized water (adjusted to pH 5.9 with malic acid) and ethanol until neutral, and dried in a vacuum drying oven at 40° C. to constant weight to obtain a functionalized copolymer with a yield of 100%. The functionalized copolymer contains 20.3 mol% p-tert-butylstyrene structures, 10.5 mol% VB-12 sulfide functional structures, and the remainder is polyisoprene. The polyisoprene structure contains 87 mol% polyisoprene 3,4 structures and 13 mol% polyisoprene 1,4 structures. The functionalized copolymer has a number average molecular weight of 95,400 g / mol and a molecular weight distribution of 1.09. The antioxidant is a 0.5% (mass fraction) ethanol solution of 2,6-di-tert-butyl-4-methylphenol.

[0107] 100 g of functionalized copolymer glue was dissolved in tetrahydrofuran, 7.1 g of iodomethane was added at 80°C for sulfonation reaction for 8 hours, filtered, and the obtained solid component was washed with cyclohexane 2 to 3 times and dried at 80°C to constant weight to obtain sulfonated antibacterial conjugated isoprene-tert-butylstyrene copolymer (denoted as TBS-IP-VB12-I) with a yield of 106.0%, a degree of sulfonation of 85%, a number average molecular weight of 101700 g / mol, and a molecular weight distribution of 1.19.

[0108] Example 8

[0109] Preparation of Quaternary Antibacterial Conjugated Piperylene-Methylstyrene Copolymer (MST-PD-VB13-Br)

[0110] An anhydrous and oxygen-free reactor was filled with high-purity nitrogen, and 2500 mL of cyclopentane, 10 mL of 0.5 M tetrahydrofuran regulator, and 10 mL of 0.5 M tert-butyl lithium initiator were added in sequence. The mixture was stirred at room temperature for 5 minutes, and then 100 g of isoprene, 350 g of p-methylstyrene, and 50 g of VB-13 amine functional monomer were added all at once. The polymerization reaction was carried out at 70-75° C. for 2 hours. The reaction was terminated by adding 2 mL of 1 M methanolic hydrochloric acid solution to obtain an amine-functionalized isoprene-p-tert-butylstyrene glue. The solution was poured into 2.5 L of ethanol containing 50 mL of an antioxidant to precipitate a copolymer. The copolymer was washed repeatedly with acidic deionized water (adjusted to pH 6.3 with citric acid) and ethanol until neutral, and dried in a vacuum drying oven at 45° C. to constant weight to obtain a functionalized copolymer with a yield of 100%. The functionalized copolymer contains 20.5 mol% p-methylstyrene structures, 10.1 mol% VB-13 amine functional structures, and the remainder is polyisoprene structures. The polyisoprene structures contain 92 mol% polyisoprene 1,4 structures and 8 mol% polyisoprene 1,2 structures. The functionalized copolymer has a number average molecular weight of 100,400 g / mol and a molecular weight distribution of 1.05. The antioxidant is a 0.5% (mass fraction) ethanol solution of 2,6-di-tert-butyl-4-methylphenol.

[0111] 100 g of functionalized copolymer glue was dissolved in tetrahydrofuran, 5.2 g of ethyl bromide was added at 80°C for quaternization reaction for 8 hours, filtered, and the resulting solid component was washed with cyclohexane 2 to 3 times and dried at 80°C to constant weight to obtain a quaternized antibacterial conjugated isoprene-methylstyrene copolymer (denoted as MST-PD-VB13-Br) with a yield of 105.0%, a degree of quaternization of 95%, a number average molecular weight of 105700 g / mol, and a molecular weight distribution of 1.15.

[0112] Example 9

[0113] Preparation of quaternary phosphine-type antibacterial conjugated S(PP')S copolymer (denoted as S-SPP'-SI)

[0114] An anhydrous and oxygen-free reactor was filled with high-purity nitrogen, and 2500 mL of cyclopentane, 0.5 M N, 10 mL of tetrahydrofuran regulator and 10 mL of 0.5 M sec-butyl lithium initiator were added in sequence. The mixture was stirred at room temperature for 5 min, and then 50 g of styrene was added first. A first-stage polymerization reaction was carried out at 60-65° C. for 0.5 h. Subsequently, 140 g of isopentadiene, 210 g of styrene and 50 g of VB-14 monomer were added. The second-stage polymerization reaction was carried out at 60-65° C. for 1 h. Then, 50 g of styrene was added. The third-stage polymerization reaction was continued at 60-65° C. for 0.5 h. Finally, 2 mL of 1 M methanolic hydrochloric acid solution was added to terminate the reaction to obtain a phosphine-functionalized S(SPP')S copolymer solution, which was poured into 2.5 L of ethanol containing 50 mL of an antioxidant to precipitate the copolymer. The product was then washed repeatedly with acidic deionized water (adjusted to pH 6.5 with malic acid) and ethanol until neutral, and dried in a vacuum oven at 45°C to constant weight to obtain a functionalized copolymer with a yield of 100%. The copolymer contained 61.5 mol% styrene structures, 9.5 mol% VB-14 phosphine-containing functional structures, and the remainder was polyisoprene structures. The polyisoprene structures contained 91 mol% polyisoprene 1,4 structures and 9 mol% polyisoprene 1,2 structures. The number-average molecular weight of the functionalized copolymer was 113,000 g / mol, with a molecular weight distribution of 1.11. The antioxidant was a 0.5% (mass fraction) ethanol solution of 2,6-di-tert-butyl-4-methylphenol.

[0115] 100 g of functionalized copolymer glue was dissolved in toluene, 5.7 g of bromobutyl was added at 80°C for quaternary phosphination reaction for 6 hours, filtered, and the resulting solid component was washed with cyclohexane 2 to 3 times and dried at 50°C to constant weight to obtain a quaternary phosphine-type antibacterial conjugated S(PP')S copolymer (denoted as S-SPP'-SI) with a yield of 105.4%, a degree of quaternization of 94%, a number average molecular weight of 119200 g / mol, and a molecular weight distribution of 1.18.

[0116] Comparative Example 1

[0117] Preparation of conjugated styrene-butadiene copolymer (SB)

[0118] An anhydrous and oxygen-free reactor was filled with high-purity nitrogen. 2500 mL of cyclohexane, 5 mL of 0.5 M potassium tert-butoxide, and 10 mL of 0.5 M n-butyl lithium initiator were added sequentially. The mixture was stirred at 50°C for 2 minutes. Then, 400 g of butadiene and 100 g of styrene were added. The reaction was allowed to proceed at 60-70°C for 1 hour. The reaction was terminated by adding 2 mL of 1 M methanolic hydrochloric acid to obtain a styrene-butadiene rubber solution. The solution was then poured into 2 L of ethanol containing 40 mL of an antioxidant to precipitate the polymer. The polymer was then dried in a vacuum drying oven to obtain a conjugated styrene-butadiene copolymer (SB) with a yield of 100%. The SB copolymer contained 85 mol% of butadiene 1,4-structures and 19.8 mol% of styrene structures. The number average molecular weight of the SB copolymer was 117,900 g / mol, with a molecular weight distribution of 1.07. The antioxidant is an ethanol solution of 2,6-di-tert-butyl-4-methylphenol with a mass fraction of 0.5%.

[0119] Test Example 1

[0120] The antibacterial tests of the conjugated diene-styrene copolymers prepared in the Examples and Comparative Examples were conducted using Escherichia coli and Staphylococcus aureus as Gram-negative and Gram-positive bacteria, respectively. The specific steps are as follows:

[0121] (1) Using a laboratory small twin-screw extruder, a conjugated diene-styrene copolymer and a PS standard resin were mixed in a mass ratio of 1:4 and extruded into granules to prepare a 20% mass fraction antibacterial masterbatch. The antibacterial masterbatch granules were blended with the PS standard resin to obtain a mixture; the mass fractions of the antibacterial masterbatch in the mixture were 1% (denoted as 1%-PS), 3% (denoted as 3%-PS), 5% (denoted as 5%-PS), and 10% (denoted as 10%-PS), respectively.

[0122] (2) Extrusion molding at 200°C and 20 MPa to obtain antibacterial plastic sheets, which are used as analysis and detection samples.

[0123] (3) Place the above sample in a porous cell culture dish and sterilize both sides with ultraviolet light. Add a standard unit of bacterial suspension and cover the bacterial suspension with a sterilized cover glass. Incubate in a 37°C incubator with a relative humidity of 90%.

[0124] (4) After 24 hours, add 1 mL of physiological saline to the multi-well culture plate with a pipette to rinse the sample surface and perform ultrasonic treatment for 1 minute. Pipette 0.1 mL of the rinse solution and dilute it with physiological saline in a gradient manner. Select the appropriate dilution and spread it on the nutrient agar plate. Incubate in a 37°C incubator for 24 hours. Select the plate with a colony count between 30 and 300 and calculate the number of viable bacteria in the sample and the antibacterial rate R. The results are shown in Table 1.

[0125] Table 1 Antibacterial test results of antibacterial plastic sheets of conjugated diene-styrene copolymers prepared in Examples and Comparative Examples

[0126]

[0127]

[0128] Note: The meaning of the antibacterial plastic sheet sample names in Table 1: Taking Example 1-1%-PS% as an example, it means that the conjugated styrene-butadiene copolymer in the antibacterial plastic sheet is prepared by Example 1, and the mass fraction of the antibacterial masterbatch is 1%.

[0129] As shown in Table 1, when the conjugated diene-styrene copolymer of the present invention is used to prepare the antibacterial polymer material with PS, a high antibacterial effect can be obtained when the antibacterial masterbatch addition amount exceeds 3wt%. When the antibacterial masterbatch addition amount exceeds 5wt%, the antibacterial rate can exceed 99%.

[0130] The above is only a preferred embodiment of the present invention. It should be pointed out that for ordinary technicians in this technical field, several improvements and modifications can be made without departing from the principles of the present invention. These improvements and modifications should also be regarded as within the scope of protection of the present invention.

Claims

1. A conjugated diene-styrene copolymer, wherein the structural units include a basic unit and a functional unit; the basic unit includes a styrene structural unit and / or a diene structural unit; the molar percentage of the functional unit in the conjugated diene-styrene copolymer is 0.1 to 25%; The functional unit has one or more structures shown in formula (5) to formula (10); in, R5 includes -H, C1~C16 alkyl, C4~C10 cycloalkyl or C6~C10 aromatic group; R6~R 10 independently include C1-C16 alkyl, C4-C10 cycloalkyl or C6-C10 aromatic groups; X is chlorine, bromine or iodine; the wavy line represents the bond to the main chain; The preparation method of the conjugated diene-styrene copolymer comprises the following steps: In anhydrous, oxygen-free and protective atmosphere, a base monomer, a functionalized monomer, a polarity modifier and a first organic solvent are mixed, and alkyl lithium is added to carry out a polymerization reaction to obtain a functionalized copolymer; the base monomer comprises a styrene monomer and / or a diene monomer; and the amount of the functionalized monomer accounts for 0.1 to 25% of the total amount of the base monomer and the functionalized monomer; The functionalized monomer includes one or more of the following structures: The functionalized copolymer is dissolved in a second organic solvent, and an active halogenated hydrocarbon is added to carry out an ionization reaction to obtain the conjugated diene-styrene copolymer; the halogen in the active halogenated hydrocarbon includes chlorine, bromine or iodine.

2. The conjugated diene-styrene copolymer according to claim 1, characterized in that: The styrene structural unit has a structure shown in formula (1); The diene structural unit has one or more structures shown in formulas (2) to (4); Wherein, R1 includes -H or C1-C4 alkyl; R2-R4 independently include -H or methyl; the wavy line represents the connection bond to the main chain; The arrangement of the basic units and the functional units includes one or more of a block sequence, a random sequence, an alternating sequence, a tapered sequence and a grafted sequence.

3. The conjugated diene-styrene copolymer according to claim 1 or 2, characterized in that: The number average molecular weight of the conjugated diene-styrene copolymer is 1-1000 kg / mol, and the molecular weight distribution is 1.02-2.

4. The method for preparing the conjugated diene-styrene copolymer according to any one of claims 1 to 3, comprising the following steps: In anhydrous, oxygen-free and protective atmosphere, a base monomer, a functionalized monomer, a polarity modifier and a first organic solvent are mixed, and alkyl lithium is added to carry out a polymerization reaction to obtain a functionalized copolymer; the base monomer comprises a styrene monomer and / or a diene monomer; and the amount of the functionalized monomer accounts for 0.1 to 25% of the total amount of the base monomer and the functionalized monomer; The functionalized monomer includes one or more of the following structures: The functionalized copolymer is dissolved in a second organic solvent, and an active halogenated hydrocarbon is added to carry out an ionization reaction to obtain the conjugated diene-styrene copolymer; the halogen in the active halogenated hydrocarbon includes chlorine, bromine or iodine.

5. The preparation method according to claim 4, characterized in that The structural formula of the styrene monomer is as follows: The structural formula of the diene monomer is as follows: The polarity regulator includes one or more of potassium alkyl alcohol, tetrahydrofuran, N,N,N',N'-tetramethylethylenediamine, tetrahydrofuran alkyl ether, ditetrahydrofurfuryl propane and N,N-dialkyltetrahydrofurfurylamine; The first organic solvent comprises one or more of cyclohexane, cyclopentane, benzene, toluene, hexane, pentane, cyclopentyl methyl ether and tetrahydrofuran; The polymerization reaction temperature is 0-100° C., and the reaction time is 0.5-12 hours.

6. The preparation method according to claim 4, characterized in that The second organic solvent includes one or more of toluene, cyclopentyl methyl ether, tetrahydrofuran, methanol, ethanol, dimethyl sulfoxide, N,N-dimethylformamide, dichloromethane and chloroform; The active halogenated hydrocarbon includes a halogenated alkyl compound or a halogenated aryl compound; The molar ratio of the functionalized monomer to the active halogenated hydrocarbon is 1:0.8-1.5; The temperature of the ionization reaction is 25 to 150° C., and the time is 0.5 to 12 hours.

7. An antibacterial polymer material comprising a conjugated diene-styrene copolymer and a polymer material, wherein the conjugated diene-styrene copolymer is the conjugated diene-styrene copolymer according to any one of claims 1 to 3 or the conjugated diene-styrene copolymer prepared by the preparation method according to any one of claims 4 to 6.

8. The antibacterial polymer material according to claim 7, characterized in that: The mass ratio of the conjugated diene-styrene copolymer to the polymer material is 1 to 10:

100.

9. The antibacterial polymer material according to claim 7 or 8, characterized in that: The polymer material includes one or more of plastic, rubber and fiber.

10. Use of the conjugated diene-styrene copolymer according to any one of claims 1 to 3, the conjugated diene-styrene copolymer prepared by the preparation method according to any one of claims 4 to 6, or the antibacterial polymer material according to any one of claims 7 to 9 in the preparation of antibacterial or antiviral agents.

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