Conjugated diene-styrene copolymer, preparation method and application thereof, antibacterial high polymer material and application thereof

Abstract

The invention provides a conjugated diene-styrene copolymer, a preparation method and application thereof, an antibacterial high polymer material and application thereof, and relates to the technical field of functional polymers. A main framework of the conjugated diene-styrene copolymer provided by the invention is provided by the styrene monomer and / or the diene monomer, the conjugated diene-styrene copolymer contains quaternary phosphorus salt, quaternary ammonium salt and sulfonium salt functional groups, and the content of the functional units can be up to 25mol%, so that the copolymer has excellent performance of inhibiting and killing bacteria, fungi and viruses; and the compound can be used as an antibacterial agent for preparing an antibacterial high polymer material with stable and lasting antibacterial performance, and can be used as an active component of antibacterial rubber, antibacterial elastomer, antibacterial resin and antibacterial paint for effectively inhibiting and killing bacteria, fungi, viruses and the like.

Description

Technical Field

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

[0002] Antibacterial and antifungal polymer materials are a new type of functional materials with bactericidal and antibacterial properties. Their core component is an antibacterial agent. A very small amount of antibacterial agent is added to the polymer material to make an antibacterial and antifungal polymer. The corresponding products also have hygienic self-cleaning functions, reducing cross-contamination caused by the use of polymer products. Organic polymer antibacterial materials are antibacterial polymers formed by antibacterial functional group monomers through polymerization or grafting. They have rich varieties, wide application range, obvious antibacterial effects, and relatively mature use technology. They have received widespread attention. Among them, the commercial products of diene-styrene copolymers include liquid rubber, thermoplastic elastomers, synthetic rubber and thermoplastic resin series products. Most of them are non-polar products and can usually be synthesized by anionic polymerization. Diene-styrene monomers can synthesize diverse sequence structures through anionic polymerization and copolymerization. At the same time, the diene microstructure has a large control range, the molecular weight can be designed, and the molecular weight distribution is very narrow. Introducing antibacterial functional groups on diene-styrene copolymers can improve the antibacterial properties of diene-styrene copolymers. 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 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 group; 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 gradual sequence and a grafted sequence.

[0012] Preferably, 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.

[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 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 active halogenated hydrocarbon is added to carry out 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 alkyl potassium 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 scheme or the conjugated diene-styrene copolymer prepared by the preparation method described in the above technical scheme.

[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, 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 performance in inhibiting and killing bacteria, fungi and viruses, and can be used as an antibacterial agent for preparing antibacterial polymer materials with stable and long-lasting antibacterial properties, and can be used as an active ingredient of antibacterial rubber, antibacterial elastomer, antibacterial resin, and antibacterial coating to 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 by an anionic copolymerization method and a post-functionalization modification method, and the ionization degree of the copolymer can be controlled, giving the material special antibacterial properties. The content of functional units in the prepared conjugated diene-styrene copolymer can be as high as 25 mol%, which can solve the problem that the content of functional groups of the conjugated diene-styrene copolymer prepared by the existing preparation method is not high, the ionization degree is limited, and thus the application field thereof is limited. Moreover, the preparation method provided by the present invention has simple process, simple operation, low cost, and is suitable for industrial production.

[0033] The conjugated diene-styrene copolymer provided by the present invention is used to prepare antibacterial polymer materials, which have 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 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 of the 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 ortho, meta or para.

[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 methyl styrene, and the substitution position of the methyl in the methyl styrene preferably includes ortho, meta or para; the C8 aromatic group preferably includes ethyl styrene and dimethyl styrene, and the substitution position of the ethyl in the ethyl styrene preferably includes ortho, meta or para, and the substitution position of the methyl in the dimethyl styrene preferably includes ortho, meta or para; the C9 aromatic group preferably includes propyl styrene or methyl-ethyl styrene; the substitution position of the propyl in the propyl styrene is preferably The preferred substitution positions include ortho, meta or para, and the propyl group preferably includes n-propyl or isopropyl; the substitution positions of the methyl and ethyl groups in the methyl-ethylstyrene preferably include ortho, meta or para; the C10 aromatic group preferably includes butylstyrene, methyl-propylstyrene or diethylstyrene; the substitution position of the butyl group in the butylstyrene preferably includes ortho, meta or para, and the butyl group preferably includes n-butyl, isobutyl or tert-butyl iso; the substitution positions of the methyl and propyl groups in the methyl-propylstyrene preferably include ortho, meta or para, and the propyl group preferably includes n-propyl or isopropyl; the substitution position of the ethyl group in the diethylstyrene preferably includes ortho, meta or para.

[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 0-99.9%, the molar percentage of the diene structural unit is preferably 0-99.9%, and the total molar percentage of the styrene structural unit and the diene structural unit is preferably 75-99.9%. In the present invention, the molar 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 molar percentage of styrene structural units in the conjugated diene-styrene copolymer is preferably 15-65%, and 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 1-1000 kg / mol, and the molecular weight distribution is preferably 1.02-2.

[0045] The main skeleton of the conjugated diene-styrene copolymer provided by the present invention is provided by styrene monomers and / or diene monomers, 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 antibacterial and sterilization properties, and can be used as an antibacterial agent for preparing antibacterial polymer materials with stable and lasting antibacterial properties, and can be used as an active ingredient of antibacterial rubber, antibacterial elastomer, antibacterial resin or antibacterial coating to 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 basic monomer, a functionalized monomer, a polarity regulator and a first organic solvent are mixed, and alkyl lithium is added to carry out polymerization reaction to obtain a functionalized copolymer; the basic monomer comprises 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;

[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 invention mixes a basic monomer, a functionalized monomer, a polarity regulator and a first organic solvent under anhydrous, oxygen-free and protective atmosphere, and adds alkyl lithium to carry out polymerization reaction to obtain a functionalized copolymer; the basic monomer comprises a styrene monomer and / or a diene monomer; and the amount of the functionalized monomer accounts for 0.1-25% 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, the diene monomer and the functional monomer is based on the molar percentage of the styrene structural unit, the diene structural unit and the 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 definitions of R6 to R in formulas (5) to (10) are the same as those of R6 to R 10The definition is the same.

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

[0060]

[0061] In the present invention, the polarity regulator preferably includes one or more of potassium alkyl alcoholate, tetrahydrofuran, N,N,N',N'-tetramethylethylenediamine, tetrahydrofuran alkyl ether, ditetrahydrofurfuryl propane and N,N-dialkyltetrahydrofurfurylamine; the potassium alkyl alcoholate preferably includes potassium tert-butoxide and / or potassium tert-amyl alcoholate. In the present invention, the molar ratio of the polarity regulator to the functional monomer is preferably 0 to 100:1, and in specific embodiments 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 1:0.0001-100, 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 polymerization reaction temperature 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 polymerization reaction time 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, and the three-stage polymerization reaction preferably includes sequentially performing a first stage polymerization reaction, a second stage polymerization reaction, and a third stage polymerization reaction. Specifically, in anhydrous, oxygen-free, and protective atmosphere, a polarity regulator, a first organic solvent, and an alkyl lithium are mixed, and part of the styrene monomer is added to perform a first stage polymerization reaction, and then a diene monomer and a functionalized monomer are added to perform a second stage polymerization reaction, and then the remaining styrene monomer is added to perform a third stage polymerization reaction. In the present invention, the mass of the part 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 0-100°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 10min-4h, and in specific embodiments it can be 10min, 15min, 0.5h, 0.75h, 1h, 1.5h, 2h, 2.5h, 3h, 3.5h or 4h. In the present invention, the temperature of the second-stage polymerization reaction is 0 to 100°C, and in specific embodiments it 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 10min to 4h, and in specific embodiments it can be 10min, 15min, 0.5h, 0.75h, 1h, 1.5h, 2h, 2.5h, 3h, 3.5h or 4h. 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 10min-4h, and in specific embodiments it can be 10min, 15min, 0.5h, 0.75h, 1h, 1.5h, 2h, 2.5h, 3h, 3.5h or 4h.

[0066] After the polymerization reaction is completed, 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, washing the copolymer with acidic water and ethanol in sequence until neutral, and drying to obtain a functionalized copolymer. 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 a specific embodiment 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 0.01-1.0 mol / L. In the present invention, the molar ratio of the functionalized monomer to the antioxidant is preferably 1:0.01-100, and in specific embodiments 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 acid, and the acid preferably includes biomass acid, and more preferably includes 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 has no special limitation on the drying time, and it can be dried to constant weight.

[0067] After obtaining the functionalized copolymer, the present invention dissolves the functionalized copolymer in a second organic solvent, adds active halogenated hydrocarbons for 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-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 may 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 25-150°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 0.5-12h, and in specific embodiments, it can be 0.5h, 1h, 2h, 3h, 4h, 5h, 6h, 7h, 8h, 9h, 10h, 11h or 12h. In the present invention, after the ionization reaction reaches a certain degree, 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 obtained ionization reaction liquid, washing the obtained solid component with cyclohexane 2 to 3 times and then drying to obtain a conjugated diene-styrene copolymer. In the present invention, the drying temperature is preferably 30 to 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 has no special limitation on the drying time, and it can be dried to constant weight.

[0073] The present invention prepares a conjugated diene-styrene copolymer by an anionic copolymerization method and a post-functionalization modification method, the ionization degree of the copolymer can be controlled, and the material is endowed with special antibacterial properties. The content of functional units in the prepared conjugated diene-styrene copolymer can be as high as 25 mol%, which can solve the problem that the content of functional groups of the conjugated diene-styrene copolymer prepared by the existing preparation method is not high, the ionization degree is limited, and thus the application field thereof is limited. Moreover, the preparation method provided by the present invention has simple process, simple operation, low cost, and is 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 scheme or the conjugated diene-styrene copolymer prepared by the preparation method described in the above technical scheme.

[0075] In the present invention, the mass ratio of the conjugated diene-styrene copolymer to the polymer material is preferably 1-10:100, more preferably 2-8:100, and in specific embodiments 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 antibacterial polymer materials, which have 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 obtained 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. In the present invention, the conjugated diene-styrene copolymer and the antibacterial polymer material are preferably used as the preparation raw materials of the antibacterial agent or the antibacterial agent; 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 the preparation raw materials of the antiviral agent; 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 and its preparation method and application, antibacterial polymer material and its application are described in detail below in conjunction with the embodiments, but they should not be construed as limiting the scope of protection of the present invention.

[0080] Example 1

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

[0082] In an anhydrous and oxygen-free reactor, high-purity nitrogen was filled, and 2500 mL of cyclohexane, 5 mL of 0.5 M potassium tert-amyl alcohol regulator and 10 mL of 0.5 M n-butyl lithium initiator were added in sequence. The mixture was stirred at room temperature for 5 min, and then 375 g of butadiene, 100 g of styrene and 25 g of VB-1 amine functional monomer were added at once. The polymerization reaction was carried out at 50-60 ° C for 2 h. 2 mL of 1 M hydrochloric acid methanol solution was added to terminate the reaction. A styrene-butadiene rubber solution with amine functionalization was obtained, and the solution was poured into 2.5 L of ethanol containing 50 mL of 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 drying oven at 40 ° C to constant weight to obtain a functionalized copolymer with a yield of 100%. The content of polybutadiene 1,4-structure, styrene structure, and VB-1 amine functional structure in the functionalized copolymer was 87 mol%, 19.8 mol%, and 5.2 mol%. 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] 100g of functionalized copolymer was dissolved in toluene, 3.9g of benzyl chloride was added at 60°C for quaternization reaction for 4h, filtered, the solid component was washed with cyclohexane 2-3 times, and dried at 60°C to constant weight to obtain quaternary antibacterial conjugated butadiene-styrene copolymer (referred to as SB-N1-Cl) with a yield of 103.6%. The degree of quaternization was 95%, the number average molecular weight was 123700g / mol, and the molecular weight distribution was 1.08.

[0084] Example 2

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

[0086] High-purity nitrogen was filled into an anhydrous and oxygen-free reactor, 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 min, and then 350 g of isoprene, 100 g of methyl styrene and 50 g of VB-3 amine functional monomer were added. The polymerization reaction was carried out at 50-60° C. for 2 h. 2 mL of 1 M hydrochloric acid methanol solution was added to terminate the reaction to obtain amine-functionalized isoprene-methyl styrene glue, which 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=6.2 with tartaric acid) and ethanol in sequence until it was 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 functional copolymer has a methylstyrene structure content of 20.5 mol%, a VB-3 amine functional structure content of 10.2 mol%, and the rest is a polyisoprene structure; the polyisoprene structure has a polyisoprene 3,4-structure content of 57 mol%, a polyisoprene 1,4-structure content of 40 mol%, and a polyisoprene 1,2-structure content of 3 mol%; the number average molecular weight of the functional copolymer is 135400 g / mol, and the molecular weight distribution is 1.06. The antioxidant is an ethanol solution of 2,6-di-tert-butyl-4-methylphenol with a mass fraction of 0.5%.

[0087] 100 g of functionalized copolymer was dissolved in cyclopentyl methyl ether, 3.0 g of ethyl bromide was added at 80°C for quaternization reaction for 5 h, filtered, the 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 amine antibacterial conjugated isoprene-styrene copolymer (denoted as SP-N5-I)

[0090] Fill the anhydrous and oxygen-free reactor with high-purity nitrogen, add 2500mL pentane, 1mL 0.5M THF regulator and 10mL 0.5M n-butyl lithium initiator in turn, stir at room temperature for 3min, then add 180g isoprene, 270g styrene and 50g VB-5 amine functional monomer at one time, react at 55-60℃ for 2h, add 2mL 1M hydrochloric acid methanol solution to terminate the reaction. Pour the amine-functionalized isoprene-styrene glue into 2.5L ethanol containing 50mL antioxidant to precipitate the copolymer. Then wash repeatedly with acidic deionized water (using malic acid to adjust pH=6.3) and ethanol to neutrality, dry in a 40℃ vacuum drying oven to constant weight, and obtain the functionalized copolymer with a yield of 100%. The functional copolymer has a styrene structure content of 55.1 mol%, a VB-5 amine functional structure content of 9.7 mol%, and the rest is a polyisoprene structure; the polyisoprene structure has a polyisoprene 1,4-structural unit content of 91 mol%, and a polyisoprene 1,2-structural unit content of 9 mol%; the molecular weight of the functional copolymer is 105900 g / mol, and the molecular weight distribution is 1.04. Among them, the antioxidant is an ethanol solution of 2,6-di-tert-butyl-4-methylphenol with a mass fraction of 0.5%.

[0091] 100 g of functionalized copolymer was dissolved in tetrahydrofuran, 3.2 g of iodomethane was added at 70°C for quaternization reaction for 3 h, filtered, the solid component was washed with cyclohexane 2 to 3 times, and dried at 50°C to constant weight to obtain a quaternary antibacterial conjugated isopentylene-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 amine antibacterial conjugated S(BN)S copolymer (denoted as SBS-N7-Cl)

[0094] Fill the anhydrous and oxygen-free reactor with high-purity nitrogen, add 2500mL hexane, 2mL 0.5M THF regulator and 10mL 0.5M sec-butyl lithium initiator in turn, stir at room temperature for 3min, then add 75g styrene, carry out a first stage polymerization reaction at 60-65℃ for 0.5h, then add 300g butadiene and 50g VB-7 monomer, carry out a second stage polymerization reaction at 60-65℃ for 0.5h, then add 75g styrene, continue a third stage polymerization reaction at 60-65℃ for 0.5h, finally add 3mL 1M hydrochloric acid methanol solution to terminate the reaction. Pour the amine-functionalized S(BN)S copolymer glue solution into 2.5L ethanol containing 50mL antioxidant to precipitate the copolymer glue. Then, the mixture was washed repeatedly with acidic deionized water (adjusted to pH=6.5 with citric acid) and ethanol until neutral, and dried in a vacuum drying oven at 45°C until constant weight, to obtain a functionalized copolymer with a yield of 100%. The functionalized copolymer contained 30.1 mol% styrene structure, 9.9 mol% VB-7 amine functional structure, and the rest was polybutadiene structure; the polybutadiene 1,4-structural unit content was 80 mol%, and the polybutadiene 1,2-structural unit content was 20 mol%; the number average molecular weight of the functionalized copolymer was 101600 g / mol, and the molecular weight distribution was 1.05. Among them, the antioxidant was an ethanol solution of 2,6-di-tert-butyl-4-methylphenol with a mass fraction of 0.5%.

[0095] 100 g of functionalized copolymer was dissolved in toluene, 3.4 g of butyl bromide was added at 70°C for quaternization reaction for 5 h, filtered, and the obtained 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 amine antibacterial conjugated S(IS')S copolymer (denoted as SIS-S8-I)

[0098] High-purity nitrogen was filled into an anhydrous and oxygen-free reactor, 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, and stirred at room temperature for 5 min. Then, 50 g of styrene was added, and a 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, and a second-stage polymerization reaction was carried out at 50-55°C for 0.75 h. Then, styrene was added. 50g of olefins, 60-65℃ for three-stage polymerization for 0.5h, finally 2mL of 1M hydrochloric acid methanol solution was added to terminate the reaction, and the sulfide-functionalized S(IS')S copolymer was obtained, which was poured into 2.5L ethanol containing 50mL of antioxidant to precipitate the copolymer, which was washed repeatedly with acidic deionized water (adjusted to pH=6.5 with citric acid) and ethanol to neutrality, and dried in a vacuum drying oven at 50℃ to constant weight to obtain a functionalized copolymer with a yield of 100%. The styrene structure content in the functionalized copolymer was 19.6mol%, the VB-8 sulfide functional structure content was 9.7mol%, and the rest was polyisoprene structure; the polyisoprene 1,4-structure content in the polyisoprene structure was 65mol%, and the polyisoprene 3,4-structure content was 35mol%; the number average molecular weight of the functionalized copolymer was 135500g / mol, and the molecular weight distribution was 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 sulfidation reaction for 5 h, filtered, and the obtained solid component was washed with cyclohexane 2 to 3 times, and dried at 70°C to constant weight to obtain a quaternary amine antibacterial conjugated S(IS')S copolymer (denoted as SIS-S8-I) with a yield of 102.9%, a degree of sulfidation 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, and stirred at room temperature for 5 min. 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. Then, the mixture was washed repeatedly with acidic deionized water (adjusted to pH=6.0 with tartaric acid) and ethanol until neutral, and dried in a vacuum drying oven at 40°C until constant weight, to obtain a functionalized copolymer with a yield of 99%. The functionalized copolymer contained 19.5 mol% styrene structure, 9.6 mol% VB-11 phosphine-containing functional structure, and the rest was polyisoprene structure; the polyisoprene structure contained 69 mol% polyisoprene 1,4-structure, and 31 mol% polyisoprene 1,2-structure; the number average molecular weight of the functionalized copolymer was 123500 g / mol, and the molecular weight distribution was 1.11. The antioxidant was an ethanol solution of 2,6-di-tert-butyl-4-methylphenol with a mass fraction of 0.5%.

[0103] 100 g of functionalized copolymer 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 obtained 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 quaternary phosphination degree of 98%, a number average molecular weight of 130800 g / mol, and a molecular weight distribution of 1.18.

[0104] Example 7

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

[0106] High-purity nitrogen was filled into an anhydrous and oxygen-free reactor, 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, and stirred at room temperature for 5 min. Then, 100 g of isoprene, 350 g of p-tert-butylstyrene and 50 g of VB-12 thioether functional structural unit were added at once, and the reaction was carried out at 50-65° C. for 2 h. 2.5 mL of 1 M hydrochloric acid methanol solution was added to terminate the reaction to obtain thioether-functionalized isoprene-p-tert-butylstyrene glue, which 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 (adjusting pH=5.9 with malic acid) and ethanol in sequence 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 functional copolymer rubber has a p-tert-butylstyrene structure content of 20.3 mol%, a VB-12 thioether functional structure content of 10.5 mol%, and the rest is a polyisoprene structure; the polyisoprene structure has a polyisoprene 3,4-structure content of 87 mol%, and a polyisoprene 1,4-structure content of 13 mol%; the functional copolymer rubber has a number average molecular weight of 95400 g / mol, and a molecular weight distribution of 1.09. The antioxidant is an ethanol solution of 2,6-di-tert-butyl-4-methylphenol with a mass fraction of 0.5%.

[0107] 100 g of functionalized copolymer was dissolved in tetrahydrofuran, 7.1 g of iodomethane was added at 80°C for sulfidation reaction for 8 h, filtered, and the obtained solid component was washed with cyclohexane 2 to 3 times, and dried at 80°C to constant weight to obtain sulfidated antibacterial conjugated isoprene-tert-butylstyrene copolymer (denoted as TBS-IP-VB12-I) with a yield of 106.0%, a degree of sulfidation 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 ammonium antibacterial conjugated isobutylene-methylstyrene copolymer (MST-PD-VB13-Br)

[0110] High-purity nitrogen was filled into an anhydrous and oxygen-free reactor, 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 min, and then 100 g of isoprene, 350 g of p-methylstyrene and 50 g of VB-13 amine functional monomer were added at once. The polymerization reaction was carried out at 70-75° C. for 2 h. 2 mL of 1 M hydrochloric acid methanol solution was added to terminate the reaction to obtain amine-functionalized isoprene-p-tert-butylstyrene glue, which was poured into 2.5 L of ethanol containing 50 mL of an antioxidant to precipitate a copolymer. The mixture was washed repeatedly with acidic deionized water (adjusted to pH=6.3 with citric acid) and ethanol in sequence 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 functional copolymer rubber contains 20.5 mol% of p-methylstyrene structure, 10.1 mol% of VB-13 amine functional structure, and the rest is polyisoprene structure; the polyisoprene structure contains 92 mol% of polyisoprene 1,4-structure and 8 mol% of polyisoprene 1,2-structure; the number average molecular weight of the functional copolymer rubber is 100400 g / mol, and the molecular weight distribution is 1.05. The antioxidant is an ethanol solution of 2,6-di-tert-butyl-4-methylphenol with a mass fraction of 0.5%.

[0111] 100 g of functionalized copolymer was dissolved in tetrahydrofuran, 5.2 g of ethyl bromide was added at 80°C for quaternization reaction for 8 h, filtered, and the obtained solid component was washed with cyclohexane 2 to 3 times, and dried at 80°C to constant weight to obtain a quaternized antibacterial conjugated isopentylene-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] High-purity nitrogen was filled into an anhydrous and oxygen-free reactor, 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, and stirred at room temperature for 5 min. Then, 50 g of styrene was added first, and a first-stage polymerization reaction was carried out at 60-65° C. for 0.5 h. Subsequently, 140 g of isopentylene, 210 g of styrene and 50 g of VB-14 monomer were added, and a second-stage polymerization reaction was carried out at 60-65° C. for 1 h. Then, 50 g of styrene was added, and a 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. Then, the mixture was washed repeatedly with acidic deionized water (adjusted to pH=6.5 with malic acid) and ethanol until neutral, and dried in a vacuum drying oven at 45°C until constant weight, to obtain a functionalized copolymer with a yield of 100%. The functionalized copolymer contained 61.5 mol% styrene structure, 9.5 mol% VB-14 phosphine-containing functional structure, and the rest was polyisoprene structure; the polyisoprene structure contained 91 mol% polyisoprene 1,4-structure, and 9 mol% polyisoprene 1,2-structure; the number average molecular weight of the functionalized copolymer was 113000 g / mol, and the molecular weight distribution was 1.11. The antioxidant was an ethanol solution of 2,6-di-tert-butyl-4-methylphenol with a mass fraction of 0.5%.

[0115] 100 g of functionalized copolymer was dissolved in toluene, 5.7 g of butyl bromide was added at 80°C for quaternary phosphination reaction for 6 hours, filtered, and the obtained 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 quaternary phosphination degree 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] In an anhydrous and oxygen-free reactor, high-purity nitrogen is filled, 2500 mL of cyclohexane, 5 mL of 0.5 M potassium tert-butoxide regulator and 10 mL of 0.5 M n-butyl lithium initiator are added in sequence, stirred at 50° C. for 2 min, then 400 g of butadiene and 100 g of styrene are added, reacted at 60-70° C. for 1 h, 2 mL of 1 M hydrochloric acid methanol solution is added to terminate the reaction, and a styrene-butadiene rubber solution is obtained, poured into 2 L of ethanol containing 40 mL of an antioxidant, a polymer is precipitated, and dried in a vacuum drying oven to obtain a conjugated styrene-butadiene copolymer (denoted as SB), with a yield of 100%. The butadiene 1,4-structure content of the conjugated styrene-butadiene copolymer is 85 mol%, and the styrene structure content is 19.8 mol%; the number average molecular weight of the conjugated styrene-butadiene copolymer is 117900 g / mol, and the molecular weight distribution is 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 test of the conjugated diene-styrene copolymer prepared in the examples and comparative examples was conducted on the samples using Escherichia coli and Staphylococcus aureus as Gram-negative bacteria and Gram-positive bacteria, respectively. The specific steps are as follows:

[0121] (1) A small laboratory twin-screw extruder was used to mix a conjugated diene-styrene copolymer and a PS standard resin in a mass ratio of 1:4, and extruded and granulated to prepare an antibacterial masterbatch with a mass fraction of 20%. 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).

[0122] (2) Extrusion molding at 200°C and 20 MPa to obtain an antibacterial plastic sheet as an analysis and detection sample.

[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 solution 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 saline to the multi-well culture plate with a pipette to rinse the sample surface and perform ultrasonic treatment for 1 minute. Use a pipette to draw 0.1 mL of the rinse solution, dilute it with saline gradient, select the appropriate dilution and smear it on the nutrient agar plate, culture it in a 37°C incubator for 24 hours, select the plate with a colony count of 30 to 300, calculate the number of live bacteria in the sample, and calculate 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: Meaning of the names of the antibacterial plastic sheet samples 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 antibacterial polymer materials with PS, a highly efficient 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 principle of the present invention. These improvements and modifications should also be regarded as the scope of protection of the present invention.

Claims

1. 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 to 25%.

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 of the structures shown in formulas (2) to (4); The functional unit has one or more structures shown in formula (5) to formula (10); 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 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 gradual 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 basic monomer, a functionalized monomer, a polarity regulator and a first organic solvent are mixed, and alkyl lithium is added to carry out polymerization reaction to obtain a functionalized copolymer; the basic monomer comprises 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; 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; 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 functionalized monomer includes one or more of the following structures: The polarity regulator includes one or more of alkyl potassium 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 described in any one of claims 1 to 3 or the conjugated diene-styrene copolymer prepared by the preparation method described in 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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