Isomonoolefine ammonium salt and phosphonium salt composite ionic polymer, preparation method and application thereof, and antibacterial polymer material

Abstract

The invention relates to the field of antibacterial functional polymer materials, and discloses an isomonoolefine ammonium salt and phosphonium salt composite ionic polymer, a preparation method and application thereof, and an antibacterial polymer material. The ionic polymer comprises a structural unit I as shown in a formula (1), a structural unit II as shown in a formula (2), a structural unit III as shown in a formula (3) and / or a formula (4) and optionally a formula (5), and a structural unit IV as shown in a formula (6) and / or a formula (7) and optionally a formula (8), the composite ionic polymer comprises a macromolecular skeleton formed by a main structure unit provided by isomonoolefine and a functional structure unit provided by aryl olefin, and meanwhile, a side chain and a main chain of the polymer contain phosphonium salt and ammonium salt functional groups at the same time, so that the polymer can be used as an antibacterial agent and is suitable for different application requirements at the same time.

Description

Technical Field

[0001] The present invention relates to the field of antibacterial functional polymer materials, and specifically, to an isomonoolefin ammonium salt phosphonium salt composite ion polymer, a preparation method and application thereof, and an antibacterial polymer material. Background Art

[0002] Since antibacterial agents or antibacterial materials can effectively inhibit the growth and spread of harmful bacteria or viruses, their applications in life are becoming increasingly widespread, including fields such as sewage purification systems, food and drug packaging and storage, daily necessities, household appliances and furniture, clothing and shoes, medical devices, and building materials. Quaternary phosphonium salt compounds are antibacterial agents with strong antibacterial properties, and have the characteristics of good stability and high and long-lasting antibacterial performance. Quaternary ammonium salt compounds are also widely used as bactericidal and bacteriostatic agents because they are not prone to generating drug resistance.

[0003] Polymeric antibacterial agents have the characteristics of high functional group density, long antibacterial effect duration, low toxicity, small irritation to the human body, high chemical stability, non-loss of antibacterial components, and non-infiltration into the epidermis of humans or animals, and have become the alternative development direction of small molecule organic antibacterial agents. Although a large number of studies have been carried out on the preparation of cationic salt antibacterial agents of the polymeric type in recent years, due to reasons such as complex preparation methods and high costs, it is difficult to achieve large-scale industrial production and be put into practical applications. Therefore, developing polymeric antibacterial materials with simple preparation processes, stability and high efficiency is of great significance for production and life.

[0004] CN102633912A discloses a preparation method of quaternized or quaternary phosphated modified chlorinated natural rubber, including the following steps: (1) dissolving chlorinated natural rubber with an organic solvent; (2) adding an organic amine compound or an organic phosphorus compound to react; (3) after reacting for 6-24 hours, cooling to room temperature and adding distilled water; (4) filtering and drying the precipitate to obtain quaternized or quaternary phosphated modified chlorinated natural rubber, which can be used to prepare antibacterial rubber or plastic products. There is no quaternized or quaternary phosphated modified halogenated butyl rubber product used to prepare antibacterial rubber or plastic products in the prior art. Summary of the Invention

[0005] The object of the present invention is to provide an isomonoolefin ammonium salt phosphonium salt composite ion polymer, a preparation method and application thereof, and an antibacterial polymer material. The composite ion polymer comprises a macromolecular skeleton composed of a main structural unit provided by an isomonoolefin and a functional structural unit provided by an aryl olefin, and simultaneously contains phosphonium salt and ammonium salt functional groups on the side chain and main chain of the polymer, so that the polymer can be used as an antibacterial agent and meet the requirements of different applications.

[0006] To achieve the above object, a first aspect of the present invention provides a composite ionic polymer of iso-monoolefin ammonium salt and phosphonium salt, characterized in that the polymer comprises structural unit I, structural unit II, structural unit III and structural unit IV;

[0007] The structural unit I has the structure shown in formula (1); the structural unit II has the structure shown in formula (2); the structural unit III has the structure shown in formula (3) and / or formula (4) and optionally the structure shown in formula (5); the structural unit IV has the structure shown in formula (6) and / or formula (7) and optionally the structure shown in formula (8);

[0008]

[0009]

[0010] wherein, R1 and R2 are each independently an alkyl group having 1 to 4 carbon atoms; R3 is an alkyl group having 1 to 4 carbon atoms; R4, R5, and R6 are each independently a straight-chain alkyl group having 1 to 20 carbon atoms, a branched-chain alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms; R7 is a methylene group; R8, R9, R 10 are each independently a straight-chain alkyl group having 1 to 10 carbon atoms, a branched-chain alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms or an aryl group having 6 to 20 carbon atoms; X is a halogen.

[0011] A second aspect of the present invention provides a method for preparing a composite ionic polymer of iso-monoolefin ammonium salt and phosphonium salt, characterized in that the preparation method comprises:

[0012] (i) Under cationic polymerization conditions, in the presence of a solvent and a catalyst, contacting an iso-monoolefin with an aryl olefin for cationic polymerization to obtain a solution containing a copolymer of the iso-monoolefin and the aryl olefin;

[0013] (ii) Subjecting the solution of the copolymer of the iso-monoolefin and the aryl olefin obtained in step (i) to a halogenation reaction with a halogenating agent to obtain a solution of a halogenated copolymer of the iso-monoolefin and the aryl olefin;

[0014] (iii) Sequentially contacting the solution of the halogenated copolymer of the iso-monoolefin and the aryl olefin obtained in step (ii) with an organic phosphorus compound and an organic amine compound to respectively carry out a first ionization reaction and a second ionization reaction to obtain a slurry-like material containing solid particles;

[0015] (iv) Carry out solid-liquid separation on the slurry-like material containing solid particles obtained in step (iii) to obtain a solid phase, and wash and dry the solid phase with a solvent to obtain the iso-monoolefin ammonium salt phosphonium salt composite ionic polymer;

[0016] Wherein, the solvent includes a halogenated alkane selected from dichloromethane and / or chloroform and at least one alkane.

[0017] The third aspect of the present invention provides an iso-monoolefin ammonium salt phosphonium salt composite ionic polymer prepared by the above preparation method.

[0018] The fourth aspect of the present invention provides an application of the above iso-monoolefin ammonium salt phosphonium salt composite ionic polymer as an antibacterial agent.

[0019] The fifth aspect of the present invention provides an antibacterial polymer material, wherein the antibacterial polymer material contains the above iso-monoolefin ammonium salt phosphonium salt composite ionic polymer.

[0020] Through the above technical solutions, the iso-monoolefin ammonium salt phosphonium salt composite ionic polymer provided by the present invention, its preparation method and application, and the antibacterial polymer material obtain the following beneficial effects:

[0021] The iso-monoolefin ammonium salt phosphonium salt composite ionic polymer provided by the present invention contains a macromolecular skeleton composed of a main structural unit provided by an iso-monoolefin and a functional structural unit provided by an aryl olefin. At the same time, phosphonium salt and ammonium salt functional groups are contained on both the side chain and the main chain of the polymer, enabling the polymer to be used as an antibacterial agent to meet the requirements of different applications.

[0022] In the preparation method of the iso-monoolefin ammonium salt phosphonium salt composite ionic polymer provided by the present invention, in the presence of a solvent of dichloromethane and / or chloroform and at least one alkane, isobutene and alkylstyrene are subjected to cationic polymerization, which can improve the polymerization activity, not only reduce the amount of activator in the catalyst, but also improve the efficiency of the halogenation reaction and reduce the occurrence of side reactions. During the ionization reaction process, the solid product always exists in the form of small particles, which is easy to remove the unreacted organic phosphine and organic amine compounds wrapped in the particles, and the product has high purity, thereby improving the thermal stability of the ionic polymer; and there is no solvent replacement process in the whole preparation process, which simplifies the production process; the obtained polymer is a composite antibacterial agent containing both phosphonium salt functional groups and ammonium salt functional groups, with better antibacterial performance, and can be used as an antibacterial agent to prepare antibacterial polymer materials with stable, durable, safe and low-toxic antibacterial properties, such as antibacterial plastics, antibacterial rubbers, antibacterial fibers and antibacterial coatings, and can effectively inhibit and kill bacteria, fungi, viruses, etc. Detailed Embodiments

[0023] The endpoints and any values in the ranges disclosed herein are not limited to the exact ranges or values, and these ranges or values should be understood to include values close to these ranges or values. For numerical ranges, the endpoint values of each range, between the endpoint values of each range and individual point values, and between individual point values can be combined with each other to obtain one or more new numerical ranges, and these numerical ranges should be regarded as specifically disclosed herein.

[0024] In the first aspect of the present invention, there is provided an isomonoolefin ammonium salt phosphonium salt composite ionic polymer, characterized in that the polymer comprises structural unit I, structural unit II, structural unit III and structural unit IV;

[0025] The structural unit I has the structure shown in formula (1); the structural unit II has the structure shown in formula (2); the structural unit III has the structure shown in formula (3) and / or formula (4) and optionally the structure shown in formula (5); the structural unit IV has the structure shown in formula (6) and / or formula (7) and optionally the structure shown in formula (8);

[0026]

[0027]

[0028] wherein, R1 and R2 are each independently an alkyl group having 1 to 4 carbon atoms; R3 is an alkyl group having 1 to 4 carbon atoms; R4, R5, R6 are each independently a straight-chain alkyl group having 1 to 20 carbon atoms, a branched-chain alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms; R7 is a methylene group; R8, R9, R 10 are each independently a straight-chain alkyl group having 1 to 10 carbon atoms, a branched-chain alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms or an aryl group having 6 to 20 carbon atoms; X is a halogen.

[0029] In the present invention, the composite ionic polymer comprises a macromolecular skeleton composed of a main structural unit provided by an isomonoolefin and a functional structural unit provided by an aryl olefin, and at the same time contains phosphonium salt and ammonium salt functional groups on both the side chain and the main chain of the polymer, so that the polymer can be used as an antibacterial agent to meet the requirements of different applications.

[0030] In the present invention, in formula (1), R1 and R2 are each independently an alkyl group having 1 to 4 carbon atoms, including methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, tert-butyl, etc., wherein, R1 and R2 can be the same or different.

[0031] In the present invention, the structural unit I shown in formula (1) is derived from an iso-olefin, and the iso-olefin includes, but is not limited to, isobutene, 2-methyl-1-butene, 2-methyl-1-pentene, 2-methyl-1-hexene, etc., and isobutene is preferred.

[0032] In the present invention, in formula (2), R3 is an alkyl group having 1 to 4 carbon atoms, including methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, tert-butyl, etc., and methyl is preferred.

[0033] Further, R4, R5, and R6 are each independently a straight-chain alkyl group having 1 to C 18 or an aryl group having 6 to 9 carbon atoms, and X is Cl or Br; further still, R4 and R5 are each independently methyl, R6 is a straight-chain alkyl group having 8 to C 16 and X is Br.

[0034] In the present invention, R7 is an alkylene group having 1 to 4 carbon atoms, including methylene, ethylene, propylene, isopropylene, butylene, isobutylene, etc., and methylene is preferred.

[0035] Further, R8, R9, and R 10 are each independently a straight-chain alkyl group having 1 to 8 carbon atoms, a branched-chain alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, or an aryl group having 6 to 8 carbon atoms, and X is Cl or Br; further still, R8, R9, and R 10 are each independently phenyl; and X is Br.

[0036] According to the present invention, based on the total molar amount of the polymer, the content of the quaternary ammonium salt group is 5 to 18 mol%; the content of the quaternary phosphonium salt group is 1 to 10 mol%.

[0037] In the present invention, when the contents of the quaternary ammonium salt group and the quaternary phosphonium salt group in the polymer each independently satisfy the above range, the antibacterial performance of the polymer can be further improved.

[0038] Further, based on the total molar amount of the polymer, the content of the quaternary ammonium salt group is 8 to 15 mol%; the content of the quaternary phosphonium salt group is 2 to 7 mol%.

[0039] According to the present invention, based on the total molar amount of the polymer, the content of the side-chain benzyl quaternary ammonium salt group is 3.5 to 12 mol%; the content of the main-chain tertiary carbon quaternary ammonium salt group is 1.5 to 6 mol%; the content of the side-chain benzyl quaternary phosphonium salt group is 0.7 to 7 mol%; the content of the main-chain tertiary carbon quaternary phosphonium salt group is 0.3 to 3 mol%.

[0040] In the present invention, when the contents of the side-chain quaternary ammonium salt and quaternary phosphonium salt groups and the main-chain tertiary carbon quaternary ammonium salt and quaternary phosphonium salt groups in the polymer satisfy the above range, the antibacterial agent has better bactericidal performance and antibacterial performance.

[0041] In the present invention, the main-chain tertiary-carbon quaternary ammonium salt group refers to the quaternary ammonium salt group on the main chain of the aryl olefin, including the structural unit shown in formula (3) and the quaternary ammonium salt group on the main chain of the aryl olefin in the structural unit shown in formula (4). In the present invention, the content of the main-chain quaternary ammonium salt group is the sum of the content of the quaternary ammonium salt group in the structural unit shown in formula (3) and the content of the quaternary ammonium salt group on the main chain in the structure shown in formula (4).

[0042] In the present invention, the side-chain quaternary ammonium salt group refers to the quaternary ammonium salt group on the side chain of the aryl olefin, including the structural unit shown in formula (5) and the quaternary ammonium salt group on the side chain of the aryl olefin in the structural unit shown in formula (4). In the present invention, the content of the side-chain benzyl quaternary ammonium salt group is the sum of the content of the quaternary ammonium salt group in the structural unit shown in formula (5) and the content of the quaternary ammonium salt group in the side chain of the structural unit shown in formula (4).

[0043] In the present invention, the main-chain tertiary-carbon quaternary phosphonium salt group refers to the quaternary phosphonium salt group on the main chain of the aryl olefin, including the structural unit shown in formula (6) and the quaternary phosphonium salt group on the main chain of the aryl olefin in the structural unit shown in formula (7). In the present invention, the content of the main-chain quaternary phosphonium salt group is the sum of the content of the quaternary phosphonium salt group in the structural unit shown in formula (6) and the content of the quaternary phosphonium salt group on the main chain in the structure shown in formula (7).

[0044] In the present invention, the side-chain quaternary phosphonium salt group refers to the quaternary phosphonium salt group on the side chain of the aryl olefin, including the structural unit shown in formula (8) and the quaternary phosphonium salt group on the side chain of the aryl olefin in the structural unit shown in formula (7). In the present invention, the content of the side-chain benzyl quaternary phosphonium salt group is the sum of the content of the quaternary phosphonium salt group in the structural unit shown in formula (8) and the content of the quaternary phosphonium salt group in the side chain of the structural unit shown in formula (7).

[0045] Further, based on the total molar amount of the polymer, the content of the side-chain benzyl quaternary ammonium salt group is 5-10 mol%; the content of the main-chain tertiary-carbon quaternary ammonium salt group is 3-5 mol%; the content of the side-chain benzyl quaternary phosphonium salt group is 1.5-5 mol%; the content of the main-chain tertiary-carbon quaternary phosphonium salt group is 0.5-2 mol%.

[0046] According to the present invention, based on the total molar amount of the polymer, the content of the structural unit I is 75-95 mol%, the content of the structural unit II is 0.5-8 mol%, the content of the structural unit III is 2.5-15 mol%, and the content of the structural unit IV is 0.5-8 mol%.

[0047] In the present invention, the iso - monoolefin ammonium salt - phosphonium salt composite ionic polymer contains structural unit III shown in formula (4) and structural unit IV shown in formula (7). Among them, structural unit III shown in formula (4) contains both a side - chain quaternary ammonium salt group and a main - chain quaternary ammonium salt group, and structural unit IV shown in formula (7) contains both a side - chain quaternary phosphonium salt group and a main - chain quaternary phosphonium salt group. Eventually, the total content of quaternary ammonium salt groups in the iso - monoolefin ammonium salt - phosphonium salt composite ionic polymer is higher than the content of structural unit III, and the total content of quaternary phosphonium salt groups is higher than the content of structural unit IV.

[0048] In the present invention, the iso - monoolefin ammonium salt - phosphonium salt composite ionic polymer has a high content of structural unit III and structural unit IV, enabling more quaternary ammonium salt and quaternary phosphonium salt functional groups to be introduced into the polymer. Eventually, the obtained polymer has a higher content of quaternary ammonium salt functional groups and quaternary phosphonium salt functional groups, and can be used as an antibacterial agent to prepare antibacterial polymer materials with stable, long - lasting, safe, and low - toxicity antibacterial properties, such as antibacterial plastics, antibacterial rubbers, antibacterial fibers, and antibacterial coatings, and can effectively inhibit and kill bacteria, especially effectively inhibit and kill Gram - negative bacteria and / or Gram - positive bacteria.

[0049] In the present invention, the total content of structural unit I, structural unit II, structural unit III, and structural unit IV is 100 mol%.

[0050] Furthermore, based on the total molar amount of the polymer, the content of structural unit I is 80 - 92 mol%, the content of structural unit II is 1 - 6 mol%, the content of structural unit III is 5 - 13 mol%, and the content of structural unit IV is 1 - 5 mol%.

[0051] According to the present invention, the thermal weight - loss temperature of 5 wt% of the iso - monoolefin ammonium salt - phosphonium salt composite ionic polymer is ≥200 °C.

[0052] In the present invention, the iso - monoolefin ammonium salt - phosphonium salt composite ionic polymer has a high thermal weight - loss temperature of 5 wt%, enabling the polymer to meet the requirements of the thermal processing conditions of polymer materials and can be directly used as an antibacterial agent in combination with polymer materials to prepare antibacterial polymer materials such as antibacterial plastics, antibacterial rubbers, antibacterial fibers, antibacterial coatings, etc.

[0053] Furthermore, the thermal weight - loss temperature of 5 wt% of the iso - monoolefin ammonium salt - phosphonium salt composite ionic polymer is ≥210 °C.

[0054] According to the present invention, based on the total weight of the iso - monoolefin ammonium salt - phosphonium salt composite ionic polymer, the Al ion content is less than or equal to 10 ppm, preferably less than or equal to 5 ppm.

[0055] The second aspect of the present invention provides a method for preparing an isomonoolefin ammonium salt phosphonium salt composite ionic polymer, characterized in that the preparation method includes:

[0056] (i) Under cationic polymerization conditions, in the presence of a solvent and a catalyst, contacting an isomonoolefin and an aryl olefin for cationic polymerization to obtain a solution containing a copolymer of the isomonoolefin and the aryl olefin;

[0057] (ii) Subjecting the solution of the copolymer of the isomonoolefin and the aryl olefin obtained in step (i) to a halogenation reaction with a halogenating agent to obtain a solution of a halogenated copolymer of the isomonoolefin and the aryl olefin;

[0058] (iii) Sequentially contacting the solution of the halogenated copolymer of the isomonoolefin and the aryl olefin obtained in step (ii) with an organic phosphorus compound and an organic amine compound to respectively carry out a first ionization reaction and a second ionization reaction to obtain a slurry-like material containing solid particles;

[0059] (iv) Carrying out solid-liquid separation on the slurry-like material containing solid particles obtained in step (iii) to obtain a solid phase, washing and drying the solid phase with a halogenated alkane to obtain the isomonoolefin ammonium salt phosphonium salt composite ionic polymer;

[0060] Wherein, the solvent includes a halogenated alkane selected from dichloromethane and / or chloroform and at least one alkane.

[0061] In the present invention, by carrying out cationic polymerization of an isomonoolefin and an aryl olefin in the presence of a solvent including a halogenated alkane selected from dichloromethane and / or chloroform and at least one alkane, it is possible to control the weight-average molecular weight of the copolymer. In particular, by controlling the sequential contact of the copolymer solution with an organic phosphorus compound and an organic amine compound, it can be ensured that during the ionization reaction, the solid product always exists in the form of small particles, which is easy to remove the unreacted organic phosphorus and organic amine compounds wrapped in the particles, thereby significantly improving the purity of the final product. Further, by using the halogenated alkane in the cationic polymerization process to wash the material, while improving the product purity, the production process is simplified; the obtained polymer is a composite antibacterial agent containing both phosphonium salt functional groups and ammonium salt functional groups, with better antibacterial performance, and can be used as an antibacterial agent to prepare antibacterial high-molecular materials with stable, lasting, safe and low-toxic antibacterial properties, such as antibacterial plastics, antibacterial rubbers, antibacterial fibers and antibacterial coatings, and can effectively inhibit and kill bacteria, fungi, viruses, etc.

[0062] According to the present invention, the volume ratio of the halogenated alkane to the alkane is 1:1 - 4.

[0063] In the present invention, when the volume ratio of the halogenated alkane to the alkane satisfies the above range, the reaction rate of cationic polymerization can be increased, the amount of the activator in the catalyst system for the cationic polymer can be reduced, and the side reactions during the halogenation reaction of the solution of the copolymer of the iso-monoolefin and the aryl olefin obtained can be significantly reduced, thereby improving the purity of the final iso-monoolefin ammonium salt phosphonium salt composite ion polymer.

[0064] Further, the volume ratio of the halogenated alkane to the alkane is 1:1.5 - 3.

[0065] In a preferred embodiment of the present invention, the solvent is dichloromethane.

[0066] In the present invention, the alkane includes aliphatic alkanes and cycloaliphatic alkanes. The aliphatic alkane is preferably an aliphatic alkane having C3 - C 10 and more preferably an aliphatic alkane having C5 - C8; the cycloaliphatic alkane is preferably a cycloaliphatic alkane having C3 - C 10 and further preferably a cycloaliphatic alkane having C5 - C8. The alkane can be one or more of n-pentane, isopentane, 2-methylpentane, 3-methylpentane, n-hexane, cyclohexane, n-heptane, isoheptane, n-octane, isooctane, and is preferably n-hexane.

[0067] In the present invention, there is no particular limitation on the amount of the solvent used, and it can be a conventional selection in the art. Generally, the amount of the solvent used is such that the total monomer concentration is 10 - 35 wt%, and more preferably 15 - 25 wt%.

[0068] In the present invention, the slurry-like material containing solid particles obtained in step (iii) is subjected to solid-liquid separation, the solvent in the material is removed to obtain a solid phase, and the solid phase is washed with a solvent, so that the unreacted organic phosphine compounds and organic amine compounds remaining in the product can be removed, and the purity of the product can be significantly improved.

[0069] According to the present invention, in the washing, the volume of the solvent is 0.5 - 2 times the volume of the solid phase.

[0070] In the present invention, when the volume of the solvent is controlled to satisfy the above range, not only can the effective removal of the organic phosphine compounds and organic amine compounds be ensured, but also the amount of the solvent used can be saved.

[0071] Further, in the washing, the volume of the solvent is 1 - 2 times the volume of the solid phase.

[0072] In the present invention, the washing is spray washing.

[0073] In the present invention, the solid-liquid separation is selected from centrifugation and / or filtration.

[0074] In a preferred embodiment of the present invention, the slurry-like material containing solid particles obtained in step (iii) is centrifuged and / or filtered using a centrifuge and / or a filter equipped with spray washing. After removing the solvent in the slurry-like material, it is then spray-washed with a halogenated alkane 1 - 3 times to remove the unreacted organic phosphine compounds and organic amine compounds remaining in the product, thereby significantly improving the purity of the product.

[0075] In the present invention, there are no specific limitations on the centrifuge and / or filter equipped with spray washing. A centrifuge with a spray washing function or a filter with a spray washing function in the prior art is applicable to the present invention. Specifically, the centrifuge with spray washing is preferably a filtering centrifuge, such as a horizontal screw filtering centrifuge, a vertical screw filtering centrifuge, a horizontal scraper discharge centrifuge, etc., and a horizontal screw filtering centrifuge is preferred. The filter with spray washing can be a filter-washing integrated machine, etc.

[0076] According to the present invention, the weight-average molecular weight of the iso-monoolefin and aryl olefin copolymer is 1×10 4 -1×10 5 g / mol, preferably 2×10 4 -8×10 4 g / mol. The molecular weight distribution of the iso-monoolefin and aryl olefin copolymer is 2 - 3.5, preferably 2.2 - 3.

[0077] According to the present invention, based on the total amount of substance of the iso-monoolefin and the aryl olefin, the molar fraction of the aryl olefin is 5 mol% - 25 mol%; preferably 8 - 20 mol%.

[0078] In the present invention, examples of the iso-monoolefin may include but are not limited to: isobutene, 2-methyl-1-butene, 2-methyl-1-pentene, 2-methyl-1-hexene, and preferably the iso-monoolefin is isobutene.

[0079] In the present invention, examples of the aryl olefin may include but are not limited to: p-methylstyrene, m-methylstyrene, p-ethylstyrene, and p-tert-butylstyrene, and preferably the aryl olefin is p-methylstyrene.

[0080] According to the present invention, the cationic polymerization conditions include: the polymerization temperature is -80°C to 0°C, preferably -60°C to -20°C; the polymerization time is 10 - 90 min, preferably 20 - 60 min.

[0081] In the present invention, there is no particular limitation on the catalyst used for cationic polymerization, and conventional cationic polymerization catalysts in the art can be employed. For example, the catalyst includes a compound capable of providing a proton, a Lewis acid, and an activator. This catalyst has high catalytic efficiency, enabling the monomer conversion rate to reach 100%, and thus can be directly used in the halogenation reaction. In the present invention, the catalyst can be a hydrogen chloride / dichloroethylaluminum / tetrachlorobenzoquinone (HCl / EADC / TCBQ) system. There is no particular limitation on the dosage of the catalyst, and it can be appropriately selected according to specific polymerization conditions so as to initiate the complete polymerization of the monomer.

[0082] In the present invention, the halogenating agent can be a substance conventional in the art that can cause some hydrogen atoms in the iso - monoolefin - aryl olefin copolymer to be replaced by halogen atoms. Preferably, the halogenating agent is a halogen element, such as bromine and / or chlorine. More preferably, the halogenating agent is bromine.

[0083] In the present invention, in step (ii), the solution of the iso - monoolefin and aryl olefin copolymer undergoes a halogenation reaction. The structural units derived from aryl olefins in the copolymer macromolecular chain undergo halogen substitution reactions, and it can cause the alkyl hydrogens on the benzene ring of the aryl olefin and the tertiary carbon hydrogens on the main chain connected to the benzene ring to undergo halogenation reactions, thereby forming side - chain alkyl halide structures and main - chain tertiary carbon halide structures in the copolymer macromolecular chain. Specifically, after halogenation, the structural units derived from aryl olefins form the following three structures:

[0084]

[0085] In the present invention, the halogenation reaction can be carried out under conventional conditions as long as it can cause the iso - monoolefin - aryl olefin copolymer to undergo halogenation. For example, the halogenation reaction is carried out in the presence of at least one radical initiator, or the halogenation reaction is carried out under photo - initiation conditions. Preferably, the halogenation reaction is carried out under photo - initiation conditions.

[0086] In the present invention, when the halogenation reaction is carried out under photo - initiation conditions, the light conditions are based on being able to initiate the halogenation reaction of the iso - monoolefin - aryl olefin copolymer. According to a preferred embodiment of the present invention, the conditions for photo - initiation include: the light wavelength is 560 - 630 nm, the light intensity is 80 - 200 mW, and the light - emitting mode is pulsed light emission. The pulsed light emission means that the light source emits light waves and stops emitting light waves at equal time intervals and alternately. Specifically, the pulse time of the pulsed light emission is 5 - 40 s, preferably 10 - 30 s.

[0087] In the present invention, there is no special limitation on the temperature of the halogenation reaction, and it can be a conventional choice; the time of the halogenation reaction can be selected according to the reaction temperature and the expected degree of halogenation reaction.

[0088] In the present invention, the amount of halogen atoms introduced into the molecular chain of the iso-olefin-aryl olefin copolymer can be selected according to the usage scenario of the finally prepared polymer. According to a preferred embodiment of the present invention, the molar ratio of the halogenating agent to the aryl olefin structural unit in the iso-olefin and aryl olefin copolymer is 1 - 1.2:1.

[0089] In the present invention, preferably, a halogenating agent, such as a halogen, is mixed with an organic solvent to obtain a halogen solution, and the halogen solution is added dropwise to the polymer solution for a halogenation reaction to achieve the regulation of the selectivity of the halogenation reaction.

[0090] In the present invention, the organic solvent is a halogenated alkane.

[0091] In a specific embodiment of the present invention, the halogen solution is slowly added dropwise to the copolymer solution, and under the irradiation of visible light emitted by an LED light source with a wavelength of 560 nm - 630 nm in a pulsed manner, a photo-halogenation reaction is carried out to obtain a halogenated copolymer solution. The structural units derived from aryl olefins in the copolymer macromolecular chain undergo halogen substitution reactions, and the alkyl hydrogens on the aryl rings of the aryl olefins and the tertiary carbon hydrogens on the main chain connected to the aryl rings can all undergo halogenation reactions, thereby forming side-chain alkyl halide structures and main-chain tertiary carbon halide structures in the polymer macromolecular chain.

[0092] In the present invention, the dropping rate of the halogen solution is 50 - 100 drops / min.

[0093] In the present invention, the dropping rate of the halogen solution is controlled so that the time of the halogenation reaction is 30 - 150 min, preferably 60 - 120 min.

[0094] In order to neutralize the hydrogen halide generated during the halogenation reaction, a certain amount of basic compounds, such as solid powders of sodium carbonate, sodium bicarbonate, calcium carbonate, magnesium carbonate, calcium oxide, magnesium oxide, etc., can be added to the copolymer solution, preferably sodium bicarbonate. The halogenated copolymer solution is centrifuged or filtered to remove the solid halogen salt compounds. The present invention has no special limitation on the centrifugation or filtration equipment, and the centrifugation or filtration equipment commonly used by those skilled in the art can be selected. The present invention has no special limitation on the centrifugation or filtration conditions, and the conditions commonly used by those skilled in the art can be adopted. According to a preferred embodiment of the present invention, a sedimentation centrifuge is selected, preferably a tubular sedimentation centrifuge.

[0095] According to the present invention, the organophosphorus compound is a tertiary phosphine compound. For example, the organophosphorus compound is selected from trimethylphosphine, triethylphosphine, tripropylphosphine, tributylphosphine, tripentylphosphine, tricyclopentylphosphine, trihexylphosphine, tricyclohexylphosphine, triheptylphosphine, trioctylphosphine, trinonylphosphine, tridecylphosphine, triphenylphosphine, etc., preferably triphenylphosphine.

[0096] According to the present invention, the molar ratio of the organic phosphine compound to the halogenating agent is 0.1 - 0.5:1.

[0097] In the present invention, when the molar ratio of the organic phosphine compound to the halogenating agent is controlled to satisfy the above range, the organic phosphine compound can be fully introduced onto the halogenated isobutene-alkylstyrene copolymer through an ionization reaction, so that the resulting iso-olefin ammonium salt phosphonium salt composite ionic polymer has a controllable content of quaternary phosphonium salt groups.

[0098] Further, the molar ratio of the organic phosphine compound to the halogenating agent is 0.2 - 0.4:1.

[0099] According to the present invention, the organic amine compound is a tertiary amine compound. For example, the organic amine compound is selected from trimethylamine, triethylamine, tripropylamine, tributylamine, tripentylamine, trihexylamine, triheptylamine, trioctylamine, trinonylamine, tridecylamine, trimethylamine, triethylamine, tripropylamine, tributylamine, tripentylamine, trihexylamine, triheptylamine, trioctylamine, trinonylamine, tridecylamine, triphenylamine, N,N-dimethylethylamine, N,N-dimethylpropylamine, N,N-dimethylbutylamine, N,N-dimethylpentylamine, N,N-dimethylhexylamine, N,N-dimethylheptylamine, N,N-dimethyloctylamine, N,N-dimethylnonylamine, N,N-dimethyldecylamine, N,N-dimethyldecylamine, N,N-dimethylundecylamine, N,N-dimethyldodecylamine, N,N-dimethyltridecylamine, N,N-dimethyltetradecylamine, N,N-dimethylpentadecylamine, N,N-dimethylhexadecylamine, N,N-dimethylheptadecylamine, N,N-dimethyloctadecylamine, N,N-dimethylnonadecylamine, N,N-dimethyleicosylamine, N,N-dimethylphenylamine, etc. Preferably, the tertiary amine is N,N-dimethylalkylamine, especially N,N-dimethyl C8-C 16 at least one of alkylamines, such as N,N-dimethyltetradecylamine.

[0100] According to the present invention, the molar ratio of the organic amine compound to the halogenating agent is 0.5 - 1:1.

[0101] In the present invention, when the molar ratio of the organic amine compound to the halogenating agent is controlled to satisfy the above range, the organic amine compound can be fully introduced onto the halogenated isobutene-alkylstyrene copolymer through an ionization reaction, so that the resulting iso-olefin ammonium salt phosphonium salt composite ionic polymer has a controllable content of quaternary ammonium salt groups.

[0102] Further, the molar ratio of the organic amine compound to the halogenating agent is 0.6 - 0.9:1.

[0103] According to the present invention, the conditions for the first ionization reaction include: reflux reaction for 2 - 10 hours under the conditions of a temperature of 60 - 120 °C and a pressure of 0.15 - 0.80 MPa.

[0104] According to the present invention, the conditions for the second ionization reaction include: reflux reaction for 6 - 15 hours under the conditions of a temperature of 60 - 120 °C and a pressure of 0.15 - 0.80 MPa.

[0105] In the present invention, when the conditions for controlling the first ionization reaction or the second ionization reaction satisfy the above ranges, the ionization reaction can have a high reaction rate, shorten the ionization reaction time, and improve the reaction efficiency of the ionization reaction.

[0106] In the present invention, preferably, the first ionization reaction and the second ionization reaction are each independently carried out in the presence of a protective gas.

[0107] In a specific embodiment of the present invention, an organophosphorus compound is added to a solution of a copolymer of a halo - isomonoolefin and an aryl olefin. In the presence of a protective gas, the first ionization reaction is carried out at a reaction temperature of 80 - 100 °C, a pressure of 0.3 - 0.5 MPa, and a reaction time of 3 - 8 h.

[0108] In a specific embodiment of the present invention, after the first ionization reaction, an organic amine compound is added. In the presence of a protective gas, the second ionization reaction is carried out at a reaction temperature of 80 - 100 °C, a pressure of 0.3 - 0.5 MPa, and a reaction time of 8 - 12 h.

[0109] In a specific embodiment of the present invention, the method further includes: adding a terminator to the solution containing the copolymer of isomonoolefin and aryl olefin obtained in step (i) to terminate the reaction.

[0110] In the present invention, there is no particular limitation on the type of the terminator, and it can be a conventional type of terminator in the art, such as triethylene glycol. There is also no particular limitation on the amount of the terminator, as long as it can terminate the polymerization reaction.

[0111] In a specific embodiment of the present invention, the method further includes: washing the terminated product with water.

[0112] In the present invention, by washing the terminated product with water, the complex formed by the termination reaction dissolved in water can be removed, and the aluminum ion content of the copolymer can be reduced.

[0113] In the present invention, the process of washing with water includes: heating the terminated product to room temperature, adding water, stirring and mixing evenly, standing for stratification, and removing the lower - layer water.

[0114] According to the present invention, the volume ratio of the water to the product after termination is 0.5 - 3:1, preferably 1 - 2:1.

[0115] According to the present invention, the time for static settling and stratification is 0.5 - 4 h, preferably 1 - 3 h.

[0116] The third aspect of the present invention provides an iso - mono - olefin ammonium salt - phosphonium salt composite ion polymer prepared by the above - mentioned preparation method.

[0117] The fourth aspect of the present invention provides an application of the above - mentioned iso - mono - olefin ammonium salt - phosphonium salt composite ion polymer as an antibacterial agent.

[0118] The fifth aspect of the present invention provides an antibacterial polymer material, which is characterized in that the antibacterial polymer material contains the above - mentioned iso - mono - olefin ammonium salt - phosphonium salt composite ion polymer.

[0119] In the present invention, the T of the iso - mono - olefin ammonium salt - phosphonium salt composite ion polymer 5wt％ The thermal weight - loss temperature reaches above 200 °C, meeting the requirements of the thermal processing technology of general polymer materials, and can be used as an antibacterial agent for preparing antibacterial polymer materials.

[0120] According to the present invention, relative to 100 parts of the polymer material, the dosage of the iso - mono - olefin ammonium salt - phosphonium salt composite ion polymer is 1 - 15 parts, preferably 4 - 10 parts.

[0121] According to the present invention, the polymer material is selected from at least one of plastics, rubbers, fibers, and coatings.

[0122] In the present invention, unless otherwise specified, the room temperature refers to 25 °C.

[0123] The present invention will be described in detail below through examples.

[0124] In the following examples, the determination of the polymer molecular weight and the molecular weight distribution index is carried out using an LC - 20A liquid - phase gel permeation chromatograph (GPC) produced by Shimadzu Corporation of Japan.

[0125] The determination of the content of each structural unit, the content of quaternary phosphonium salt and quaternary ammonium salt in the copolymer is carried out using an AVANCE400 nuclear magnetic resonance spectrometer produced by Bruker Corporation of Switzerland.

[0126] The method for determining the polymerization conversion rate: the ratio of the mass of the polymer obtained after polymerization to the mass of the monomers added.

[0127] The content of metal Al element in the sample is determined using an inductively coupled plasma atomic emission spectrometer (ICP - OES), and the execution standard is JYT015 - 1996.

[0128] The thermogravimetric test of the sample was carried out using a METTLER TGA / DSC1 instrument. The test temperature range was 25 - 600 °C, the heating rate was 10 °C / min, and the nitrogen atmosphere was 50 mL / min.

[0129] Example 1

[0130] (1) 0.8 L of dichloromethane, 1.2 L of hexane, and 5.5 mol of isobutene (IB) and 1.1 mol of p-methylstyrene (p-MeSt) were sequentially added to a 10 L polymerization kettle equipped with a stirrer, a jacket, and an internal cooling tube. Based on the total amount of isobutene and alkylstyrene, the molar fraction of alkylstyrene was 16.7 mol%. The stirring was started and the mixture was evenly mixed. The temperature of the monomer solution was lowered to -40 °C using the coolant in the jacket and the internal cooling tube. 60 mL of the aged catalyst (HCl / EADC / TCBQ) solution (the molar ratio of HCl / EADC / TCBQ was 0.2:1:0.1) was slowly added, and the polymerization reaction temperature was controlled at -40 ± 2 °C using the coolant in the jacket and the internal cooling tube of the polymerization kettle. After 40 min of polymerization reaction, 10 mL of the terminator solution (a dichloromethane solution of triethylene glycol with a concentration of 2 wt%) was added. Among them, the volume ratio of dichloromethane to hexane was 1:1.5, and the monomer concentration was 20 wt%.

[0131] (2) The polymer solution was heated to 30 °C, 2.8 L of water (the volume ratio of water to the product of step (1) was 1:1) was added, and after stirring and mixing for 10 min, it was allowed to stand and separate for 2 h, and the lower layer of water was drained. 110 g of sodium bicarbonate powder (the molar ratio of sodium bicarbonate to bromine was 1.1:1) was added.

[0132] (3) 68 mL of bromine was added to a constant-pressure dropping funnel containing 200 mL of dichloromethane (the molar ratio of bromine to p-methylstyrene in the polymer was 1.1:1). The photobromination reaction was carried out under irradiation with a 595 nm light source, the light source intensity was 100 mW, and the pulse time was 20 s. The light source was turned on for the bromination reaction, and the bromine solution was added at a rate of 60 drops / min. After the bromine solution was added dropwise, the reaction was continued for 5 minutes, the light source was turned off, and the reaction was stopped. The bromination reaction time was 90 min.

[0133] (4) The brominated polymer solution was separated by a tubular settling centrifuge to remove the insoluble precipitate therein. The obtained clear liquid was transferred to a 5L pressure-resistant glass stirring kettle with a jacket, the stirring was started, and 0.10 kg of triphenylphosphine was added (the molar ratio of triphenylphosphine to liquid bromine was 0.3:1). The reaction system was heated to 90 °C, the reaction pressure was maintained at 0.40 MPa, and the reflux reaction was carried out for 4 h to obtain a slurry-like material. Then 0.25 kg of N,N-dimethyltetradecylamine was added (the molar ratio of N,N-dimethyltetradecylamine to liquid bromine was 0.8:1), and the reflux reaction was continued at the reaction temperature of 90 °C and the reaction pressure of 0.40 MPa for 10 h to obtain a slurry-like material.

[0134] (5) The solvent was removed by centrifugal separation using a horizontal spiral filter centrifuge, and the solid particles were spray-washed with fresh solvent dichloromethane and then separated. The volume of the fresh solvent was 1.2 times the volume of the solid particles after the solvent was removed, and the number of washing times was 2 times.

[0135] The obtained solid particles were vacuum-dried at 40 °C for 6 h to obtain polymer A1. Polymer A1 was analyzed for molecular weight and distribution, nuclear magnetic resonance, Al ion content, and thermal weight loss temperature. The results are shown in Table 2.

[0136] Examples 2 - 9

[0137] The isomonoolefin ammonium salt phosphonium salt composite ion polymer was prepared according to the method of Example 1, except that: the amounts of materials in each step and the specific process conditions were different from those in Example 1, as shown in Table 1 specifically. The test results are shown in Table 2.

[0138] Comparative Example 1

[0139] The isomonoolefin ammonium salt phosphonium salt composite ion polymer was prepared according to the method of Example 1, except that: there was no spray-washing process in step (5), and it was directly dried after centrifugally separating and removing the solvent, as shown in Table 1 specifically. The test results are shown in Table 2.

[0140] Comparative Example 2

[0141] The isomonoolefin ammonium salt phosphonium salt composite ion polymer was prepared according to the method of Example 1, except that: the solvent used in step (1) was n-hexane, as shown in Table 1 specifically. The test results are shown in Table 2.

[0142] Comparative Example 3

[0143] The isomonoolefin ammonium salt phosphonium salt composite ion polymer was prepared according to the method of Example 1, except that: in step (4), N,N-dimethyltetradecylamine was added first, and then triphenylphosphine was added, as shown in Table 1 specifically. The test results are shown in Table 2.

[0144] Table 1

[0145]

[0146]

[0147] a Refers to the conversion rate of cationic polymerization.

[0148]

[0149]

[0150] Table 2 Iso - monoolefin - aryl olefin copolymer

[0151] Weight-average molecular weight of polymer Molecular weight distribution of polymer Mole fraction of p-MeSt in polymer, mol% Example 1 45800 2.61 16.7 Example 2 46100 2.58 16.7 Example 3 44820 2.41 16.7 Example 4 47120 2.54 16.7 Example 5 43960 2.51 16.7 Example 6 45100 2.67 16.7 Example 7 45740 2.36 16.7 Example 8 41640 2.47 16.7 Example 9 46600 2.54 16.7 Comparative Example 1 43820 2.55 16.7 Comparative Example 2 42960 2.63 16.7 Comparative Example 3 45340 2.60 16.7

[0152] Table 2 continued Iso - monoolefin ammonium salt - phosphonium salt composite ionic polymer

[0153]

[0154] Table 2 continued

[0155] Structural unit I Structural unit II Structural unit III Structural unit IV mol% mol% mol% mol% Example 1 83.3 3 9.6 4.1 Example 2 83.3 3.1 9.5 4.1 Example 3 83.3 3.2 9.4 4.1 Example 4 83.3 3 7.9 5.8 Example 5 83.3 3 11.2 2.5 Example 6 83.3 3 9.6 4.1 Example 7 83.3 3 9.6 4.1 Example 8 83.3 4 8.6 4.1 Example 9 83.3 6.2 7.5 3 Comparative Example 1 83.3 3 9.6 4.1 Comparative Example 2 83.3 4.2 8.4 4.1 Comparative Example 3 83.3 3.1 9.6 4.0

[0156] Table 2 continued Iso - monoolefin ammonium salt - phosphonium salt composite ionic polymer

[0157]

[0158]

[0159] As can be seen from Table 1 and Table 2, compared with Comparative Example 1, after solid - liquid separation of the obtained slurry - like material in Examples 1 - 9 of the present invention, the solid phase was washed, and unreacted organophosphorus compounds and organic amine compounds were fully removed, significantly improving the purity of the polymer, and thus increasing the 5wt% thermal weight - loss temperature of the polymer.

[0160] Compared with Comparative Example 2, in Examples 1 - 9 of the present invention, a mixed solvent of dichloromethane and n - hexane was used as the solvent for cationic polymerization. During the halogenation process, the halogen utilization rate was high, enabling more cationic salt functional groups (quaternary ammonium salt groups and quaternary phosphonium salt groups) to be introduced during the ionization process, which could further improve the antibacterial performance of the polymer.

[0161] The cationic salt polymer obtained in Comparative Example 3 was in a lump shape. Compared with Comparative Example 3, the cationic salt polymers obtained in Examples 1 - 9 of the present invention were in small particle shapes, and unreacted organophosphorus and organic amine compounds could be fully removed during the washing process, with high polymer purity, resulting in an increase in the 5wt% thermal weight - loss temperature of the polymer.

[0162] Compared with Examples 1-7, in Example 8, due to the higher proportion of alkanes in the mixed solvent, halogenation occurred between the halogen and the alkane solvent during the halogenation process, resulting in a decrease in the utilization rate of the halogen, and ultimately leading to a lower content of cationic salt functional groups (quaternary ammonium salt groups and quaternary phosphonium salt groups) introduced into the ionic polymer, which is unfavorable for the antibacterial performance.

[0163] Compared with Examples 1-7, in Example 9, due to the lower ionization reaction temperature and slow ionization reaction, the content of cationic salt functional groups (quaternary ammonium salt groups and quaternary phosphonium salt groups) introduced into the ionic polymer is lower, which is unfavorable for the antibacterial performance.

[0164] The preferred embodiments of the present invention are described in detail above, but the present invention is not limited thereto. Within the technical concept of the present invention, the technical solution of the present invention can be subjected to a variety of simple modifications, including the combination of various technical features in any other suitable manner, and these simple modifications and combinations should also be regarded as the contents disclosed by the present invention and belong to the protection scope of the present invention.

Claims

1. An isomonoolefin ammonium salt phosphonium salt composite ionic polymer, characterized in that The polymer includes structural unit I, structural unit II, structural unit III and structural unit IV; The structural unit I has the structure shown in formula (1); the structural unit II has the structure shown in formula (2); the structural unit III has the structure shown in formula (3) and / or formula (4) and optionally the structure shown in formula (5); the structural unit IV has the structure shown in formula (6) and / or formula (7) and optionally the structure shown in formula (8); wherein, R1 and R2 are each independently a C1-C4 alkyl group; R3 is a C1-C4 alkyl group; R4, R5, and R6 are each independently a straight-chain C1-C 20 alkyl group, a branched-chain C1-C 20 alkyl group, or a C6-C 20 aryl group; R7 is a methylene group; R8, R9, and R 10 are each independently a straight-chain C1-C 10 alkyl group, a branched-chain C1-C 10 alkyl group, a C3-C 10 cycloalkyl group, or a C6-C 20 aryl group; X is a halogen.

2. The iso-olefin ammonium salt phosphonium salt composite ionic polymer according to claim 1, wherein Based on the total molar amount of the polymer, the content of the quaternary ammonium salt group is 5-18 mol%, preferably 8-15 mol%; the content of the quaternary phosphonium salt group is 1-10 mol%, preferably 2-7 mol%; Preferably, R1 and R2 are each independently methyl; R3 is methyl; R4 and R5 are each independently methyl, and R6 is a straight-chain alkyl group having 8 to C 16 ; R7 is methylene; R8, R9, R 10 are each independently phenyl; and X is Cl or Br.

3. The iso - monoolefin ammonium salt - phosphonium salt composite ionic polymer according to claim 1 or 2, wherein, Based on the total molar amount of the polymer, the content of the side-chain benzyl quaternary ammonium salt group is 3.5-12 mol%, preferably 5-10 mol%; the content of the main-chain tertiary carbon quaternary ammonium salt group is 1.5-6 mol%, preferably 3-5 mol%; the content of the side-chain benzyl quaternary phosphonium salt group is 0.7-7 mol%, preferably 1.5-5 mol%; the content of the main-chain tertiary carbon quaternary phosphonium salt group is 0.3-3 mol%, preferably 0.5-2 mol%.

4. The iso - mono - olefin ammonium salt - phosphonium salt composite ionic polymer according to any one of claims 1 - 3, wherein, Based on the total molar amount of the polymer, the content of the structural unit I is 75-95 mol%, the content of the structural unit II is 0.5-8 mol%, the content of the structural unit III is 2.5-15 mol%, and the content of the structural unit IV is 0.5-8 mol%; Preferably, based on the total molar amount of the polymer, the content of the structural unit I is 80-92 mol%, the content of the structural unit II is 1-6 mol%, the content of the structural unit III is 5-13 mol%, and the content of the structural unit IV is 1-5 mol%.

5. The iso - mono - olefin ammonium salt phosphonium salt composite ionic polymer according to any one of claims 1 - 4, wherein, The thermal weight loss temperature of 5 wt% of the iso-olefin ammonium salt phosphonium salt composite ion polymer ≥ 200 °C, preferably ≥ 210 °C; Preferably, based on the total weight of the iso-olefin ammonium salt phosphonium salt composite ion polymer, the content of Al ions is less than or equal to 10 ppm, preferably less than or equal to 5 ppm.

6. A preparation method of an isomonoolefin ammonium salt phosphonium salt composite ionic polymer, characterized in that, The preparation method includes: (i) Under cationic polymerization conditions, in the presence of a solvent and a catalyst, an iso-olefin and an aryl olefin are contacted for cationic polymerization to obtain a solution containing a copolymer of the iso-olefin and the aryl olefin; (ii) The solution of the copolymer of the iso-olefin and the aryl olefin obtained in step (i) is subjected to a halogenation reaction with a halogenating agent to obtain a solution of a halogenated copolymer of the iso-olefin and the aryl olefin; (iii) The solution of the halogenated copolymer of the iso-olefin and the aryl olefin obtained in step (ii) is successively contacted with an organic phosphorus compound and an organic amine compound to carry out a first ionization reaction and a second ionization reaction respectively to obtain a slurry-like material containing solid particles; (iv) The slurry-like material containing solid particles obtained in step (iii) is subjected to solid-liquid separation to obtain a solid phase, and the solid phase is washed and dried with a solvent to obtain the iso-olefin ammonium salt phosphonium salt composite ion polymer; Among them, the solvent includes a halogenated alkane selected from methylene chloride and / or chloroform and at least one alkane.

7. The preparation method according to claim 6, wherein, The volume ratio of the halogenated alkane to the alkane is 1:1 - 4; Preferably, in the washing, the volume of the solvent is 0.5 - 2 times the volume of the solid phase; Preferably, the washing is spray washing; Preferably, the number of washing times is 1 - 3 times; Preferably, the solid-liquid separation is selected from centrifugation and / or filtration.

8. The preparation method according to claim 6 or 7, wherein The weight-average molecular weight of the iso-olefin and aryl olefin copolymer is 1×10 4 -1×10 5 g / mol; Preferably, based on the total amount of substance of the iso-monoolefin and the aryl olefin, the molar fraction of the aryl olefin is 5 mol% - 25 mol%; Preferably, the cationic polymerization conditions include: the polymerization temperature is -80 °C to 0 °C, preferably -60 °C to -20 °C; the polymerization time is 10 - 90 min, preferably 20 - 60 min.

9. The preparation method according to any one of claims 6-8, wherein, The halogenating agent is a halogen element, preferably bromine; Preferably, the halogenation reaction is carried out under photo-initiated conditions; Preferably, the conditions of the halogenation reaction include: the halogenation reaction time is 30 - 150 min, preferably 60 - 120 min; Preferably, the molar ratio of the halogenating agent to the aryl olefin structural unit in the copolymer of iso-monoolefin and aryl olefin is 1 - 1.2:

1.

10. The preparation method according to any one of claims 6-9, wherein, The organic phosphine compound is a tertiary phosphine compound; Preferably, the molar ratio of the organic phosphine compound to the halogenating agent is 0.1 - 0.5:1; Preferably, the organic amine compound is a tertiary amine compound; Preferably, the molar ratio of the organic amine compound to the halogenating agent is 0.5 - 1:1; Preferably, the conditions of the first ionization reaction include: reflux reaction for 2 - 10 hours under the conditions of a temperature of 60 - 120 °C and a pressure of 0.15 - 0.80 MPa; Preferably, the conditions of the second ionization reaction include: reflux reaction for 6 - 15 hours under the conditions of a temperature of 60 - 120 °C and a pressure of 0.15 - 0.80 MPa.

11. The preparation method according to any one of claims 6-10, wherein, The method further includes: adding a terminator to terminate in the solution containing the copolymer of iso-monoolefin and aryl olefin obtained in step (i); Preferably, the method further includes: washing the terminated product with water; Preferably, the process of the water washing includes: heating the terminated product to room temperature, adding water, stirring and mixing evenly, then standing for stratification, and removing the lower layer of water; Preferably, the volume ratio of the water to the terminated product is 0.5 - 3:1, preferably 1 - 2:1; Preferably, the standing time for stratification is 0.5 - 4 h, preferably 1 - 3 h.

12. An iso-monoolefin ammonium salt phosphonium salt composite ionic polymer prepared by the preparation method according to any one of claims 6 - 11.

13. Use of the iso-monoolefin ammonium salt phosphonium salt composite ionic polymer according to any one of claims 1 - 5 and 12 as an antibacterial agent.

14. An antibacterial polymer material, characterized in that, The antibacterial polymer material contains the iso-monoolefin ammonium salt phosphonium salt composite ionic polymer according to any one of claims 1 - 5 and 12; Preferably, relative to 100 parts of the polymer material, the dosage of the iso-monoolefin ammonium salt phosphonium salt composite ionic polymer is 1 - 15 parts, preferably 4 - 10 parts; Preferably, the polymer material is selected from at least one of plastics, rubbers, fibers, and coatings.

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