Reaction activity branched isobutenyl composite cationic salt copolymer, preparation method thereof and antibacterial coating

Abstract

The invention relates to the field of antibacterial functional high polymer materials, and discloses a reaction active branched isobutenyl composite cationic salt copolymer, a preparation method thereof and an antibacterial coating. The copolymer has a star-shaped branched structure comprising a plurality of branched chains; the branched chain isobutene comprises a structural unit and a structural unit I shown in a formula I; # imgabs0 # R is a C1-C4 alkylene group, Q1 and Q2 are each independently selected from H, a reactive functional group or a cationic salt group, and Q1 and Q2 in the copolymer are not both H at the same time. The copolymer has a star-shaped branched structure comprising a plurality of branched chains, and the branched chain structure simultaneously contains cationic salt groups and reaction active functional groups, so that the copolymer has excellent antibacterial performance, also has the capability of co-crosslinking and curing with coating resin, not only has good compatibility with the coating resin, but also has good antibacterial property. And the adhesive property of a coating material and the surface of a base material can be remarkably improved.

Description

Technical Field

[0001] The invention relates to the field of antibacterial functional polymer materials, and in particular to a reactive branched isobutylene-based composite cationic salt copolymer and a preparation method thereof, and an antibacterial coating. Background Art

[0002] In recent years, with the continuous improvement of people's antibacterial awareness, antibacterial materials have been more and more widely used, especially antibacterial coating materials. Because they can effectively inhibit the reproduction and spread of pathogens, antibacterial coatings have shown a strong development trend and are widely used in food and drug processing industries, hospitals, schools and other crowded public places.

[0003] At present, most antibacterial coatings use metal ions or metal oxides as bactericide components, which are made into nanoparticles and added to the coating. Among them, silver ions are the main bactericides and are the mainstream application of antibacterial coatings. This kind of nano silver ion antibacterial agent not only has high production costs, but also has problems that need to be solved in terms of uniform dispersion in the coating and prevention of agglomeration in order to maintain good storage stability of the coating.

[0004] Metal antimicrobial agents are inorganic filler ingredients, and it is necessary to consider that the metal-carrying fillers will not significantly affect the mechanical properties of the coating. The bactericidal mechanism of metal ions is diffusion sterilization to the coating surface, which not only requires controlling the diffusion rate of metal ions, but also as metal ions are continuously released into the environment, the antibacterial properties of the coating continue to decay, and the stability and durability of the antibacterial properties cannot be maintained. In addition, the antibacterial coating materials used in some special environments, such as various complex water system environments, not only have the problem of releasing metal toxic materials into the water system, but the microorganisms in the water system are also very complex, which will lead to poor antibacterial and antifouling effects of the coating.

[0005] Compared with metal antimicrobial agents, polymer antimicrobial agents have the characteristics of non-migration, non-release, safety, low toxicity, stable, high efficiency and long-lasting antimicrobial performance, making antimicrobial coatings safer, environmentally friendly, green and low-cost, with a wider range of applicability, and are an important development direction for antimicrobial coatings.

[0006] Cationic salt copolymers are not only highly effective surfactants and antistatic agents, but also quaternary ammonium salts and quaternary phosphonium salts are widely used because of their more efficient and broad-spectrum antibacterial properties. Isobutylene-based cationic salt copolymers are safe, low-toxic, aging-resistant, weather-resistant, chemically stable, and have excellent bonding properties, and show good application prospects in the field of medical and sanitary materials.

[0007] Paint is a resin solution system that is cross-linked and cured at low temperature. The degree of cross-linking and curing of the resin is an important factor affecting the mechanical properties of the coating. The widely used metal nanofiller antibacterial agent is a filling component of the filler. It not only cannot improve the mechanical properties of the paint, but may also cause the paint performance to decline. Summary of the invention

[0008] The purpose of the present invention is to overcome the problem that the conventional antibacterial agent for coatings in the prior art leads to insufficient durability of the antibacterial performance of the coatings and reduced mechanical properties, and to provide a reactive branched isobutylene-based composite cationic copolymer and a preparation method thereof, and an antibacterial coating. The copolymer has a star-shaped branched structure including multiple branches, and the branched structure simultaneously carries a cationic salt group and a reactive functional group, which can make the copolymer have excellent antibacterial properties and the ability to be cross-linked and cured with the coating resin, and not only has good compatibility with coating resins such as polyester resins, polyurethane resins, polyacrylic resins, epoxy resins, alkyd resins, amino resins, etc., but also can significantly improve the bonding performance between the coating material and the substrate surface, and is applicable to a wide range of substrates, including plastics, glass, wood, metal, ceramics, concrete, etc.

[0009] In order to achieve the above-mentioned object, the first aspect of the present invention provides a reactive branched isobutylene-based composite cationic salt copolymer, wherein the copolymer has a star-branched structure including a plurality of branches;

[0010] The branched chain includes an isobutylene structural unit and a structural unit I shown in formula I;

[0011]

[0012] R is C 1 -C 4 The alkylene group, Q 1 and Q 2 Each is independently selected from H, a reactive functional group or a cationic salt group, and in the copolymer Q 1 and Q 2 Not all are H at the same time.

[0013] The second aspect of the present invention provides a method for preparing a reactive branched isobutylene-based composite cationic salt copolymer, wherein the preparation method comprises:

[0014] (1) contacting and mixing an initiator solution and a monomer solution in a microchannel reaction under cationic polymerization conditions to perform a cationic polymerization reaction to obtain a solution containing a branched isobutylene-alkylstyrene copolymer;

[0015] (2) contacting the solution of the branched isobutylene-alkylstyrene copolymer with a halogen to carry out a halogenation reaction to obtain a solution containing a halogenated branched isobutylene-based copolymer;

[0016] (3) adding a phosphine compound to the solution of the halogenated branched isobutylene-based copolymer to carry out a first ionization reaction, and then adding a nitrogen compound to carry out a second ionization reaction to obtain a solution containing a branched isobutylene-based composite cationic salt copolymer;

[0017] (4) adding a compound having an active functional group to the solution of the branched isobutylene-based composite cationic salt copolymer to carry out an active functionalization reaction to obtain the reactive branched isobutylene-based composite cationic salt copolymer;

[0018] The initiator solution comprises at least one multifunctional initiator, at least one activator, at least one co-initiator and at least one halogenated alkane.

[0019] The third aspect of the present invention provides a reactive branched isobutylene-based composite cationic salt copolymer prepared by the above preparation method.

[0020] A fourth aspect of the present invention provides an antibacterial coating, wherein the antibacterial coating comprises the above-mentioned reactive branched isobutylene-based complex cationic salt copolymer and a coating resin.

[0021] Through the above technical scheme, the reactive branched isobutylene-based composite cationic salt copolymer and its preparation method and antibacterial coating provided by the present invention achieve the following beneficial effects:

[0022] In the present invention, the reactive branched isobutylene-based composite cationic salt copolymer has a star-branched structure including multiple branches, and the branched structure carries both cationic salt groups and reactive functional groups, which enables the copolymer to have excellent antibacterial properties and co-crosslinking and curing capabilities with coating resins. When used in coatings, it can impart excellent and lasting antibacterial properties to the coating material while significantly improving the bonding performance between the coating material and the surface of the substrate.

[0023] Furthermore, the copolymer of the present invention has a low weight average molecular weight and a high styrene content (structural unit I shown in formula I), which enables the copolymer to have good compatibility with the coating resin.

[0024] Furthermore, the copolymer of the present invention contains a high content of cationic salt groups, which can significantly improve the water solubility and water dispersion stability of the copolymer, and make the aqueous solution containing the copolymer have a lower solution viscosity, which is more suitable for water-based resins and water-based coatings.

[0025] Furthermore, the copolymer described in the present invention contains a relatively high content of reactive functional groups, which can be cross-linked and cured with coating resins to serve as adhesives for coating filling components, including polyester resins, polyurethane resins, polyacrylic resins, epoxy resins, alkyd resins, amino resins, etc., and significantly improve the bonding performance between the coating material and the substrate surface, and are applicable to a wide range of substrates, including plastics, glass, wood, metal, ceramics, concrete, etc.

[0026] In the preparation method of the reactive branched isobutylene-based composite cationic salt copolymer, in the presence of a multifunctional initiator, a cationic polymerization reaction of isobutylene and alkylstyrene is carried out in a microchannel reactor to obtain an isobutylene-alkylstyrene copolymer with a branched structure, and a reactive branched isobutylene-based composite cationic salt copolymer is obtained through a halogenation reaction, an ionization reaction and a functionalization reaction. The copolymer has a star-shaped branched structure including a plurality of branches, and the branched structure carries a cationic salt group and a reactive functional group at the same time, so that the copolymer has excellent antibacterial properties and cross-linking and curing capabilities. When the copolymer is used in a coating, it can give the coating material excellent and lasting antibacterial properties and significantly improve the bonding performance between the coating material and the surface of the substrate. BRIEF DESCRIPTION OF THE DRAWINGS

[0027] Figure 1 This is a simplified diagram of the process for preparing branched isobutylene-based copolymers.

[0028] Description of Reference Numerals

[0029] 1: initiator solution; 2: monomer solution; 3: feed pump; 4: microchannel reactor; 4-1 to 4-10: reaction module; 5: tubular reactor; 6: water washing kettle; 7: deionized water; 8: copolymer solution; 9: wastewater DETAILED DESCRIPTION

[0030] The endpoints and any values ​​of the ranges disclosed in this article are not limited to the precise 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, the endpoint values ​​of each range and the individual point values, and the individual point values ​​can be combined with each other to obtain one or more new numerical ranges, which should be considered as specifically disclosed in this article.

[0031] The first aspect of the present invention provides a reactive branched isobutylene-based composite cationic salt copolymer, wherein the copolymer has a star-branched structure including a plurality of branches;

[0032] The branched chain includes an isobutylene structural unit and a structural unit I shown in formula I;

[0033]

[0034] R is C 1 -C 4 The alkylene group, Q 1 and Q 2 Each is independently selected from H, a reactive functional group or a cationic salt group, and in the copolymer Q 1 and Q 2 Not all are H at the same time.

[0035] In the present invention, the copolymer has a star-branched structure including multiple branches, and the branched structure carries both cationic salt groups and reactive functional groups, which enables the copolymer to have excellent antibacterial properties and co-crosslinking and curing capabilities with the coating resin. When used in coatings, it can impart excellent and lasting antibacterial properties to the coating material while significantly improving the bonding performance between the coating material and the substrate.

[0036] In the present invention, the star-shaped branched structure with multiple branches refers to a star-shaped structure with multiple central divergent branches.

[0037] In the present invention, the copolymer Q 1 and Q 2 Not all H at the same time means that there is no Q in each macromolecule of the copolymer. 1 and Q 2 All are H, but Q can exist in some segments of the molecular chain of the copolymer 1 and Q 2 At the same time, it is the case of H.

[0038] Furthermore, R is a methylene group or an ethylene group, preferably a methylene group.

[0039] According to the present invention, based on the total molar amount of the copolymer, the content of the isobutylene structural unit is 55-80 mol%.

[0040] In the present invention, the copolymer has a low weight average molecular weight and a high styrene content (structural unit I shown in formula I), which enables the copolymer to have good compatibility with the coating resin.

[0041] Furthermore, based on the total molar amount of the copolymer, the content of the isobutylene structural unit is 60-75 mol%.

[0042] According to the present invention, based on the total molar amount of the copolymer, the content of the cationic salt group is 5-25 mol%.

[0043] In the present invention, the copolymer contains a high content of cationic salt groups, which can significantly improve the water solubility and water dispersion stability of the copolymer, and make the aqueous solution containing the copolymer have a lower solution viscosity, which is more suitable for water-based resins and water-based coatings.

[0044] Furthermore, based on the total molar amount of the copolymer, the content of the cationic salt group is 8-20 mol%.

[0045] According to the present invention, the cationic salt groups are nitrogen salt groups and phosphonium salt groups.

[0046] In the present invention, the nitrogen salt group has a structure shown in formula (1) or a structure shown in formula (2);

[0047] Among them, R 1 , R 2 , R 3 Each independently is C 1 -C 20 Straight chain alkyl, C 1 -C 20 Branched alkyl, C 3 -C 10 Cycloalkyl or C 6 -C 10 The aryl group; R 4 , R 5 , R 6 , R 7 are independently hydrogen, a halogen atom, C 1 -C 10 Straight chain alkyl, C 1 -C 10 branched alkyl, hydroxyl, nitro; X ​​is Cl or Br.

[0048] Furthermore, R 1 and R 2 is methyl, R 3 C 4 -C 18 A straight chain alkyl group; R 4 , R 5 , R 6 , R 7 are independently hydrogen, C 1 -C 4 A straight-chain alkyl group or a nitro group; X is Br.

[0049] In the present invention, the phosphonium salt has a structure shown in formula (3);

[0050] Among them, R 8 , R 9 , R 10Each independently is C 1 -C 10 Straight chain alkyl, C 1 -C 10 Branched alkyl, C 3 -C 10 Cycloalkyl or C 6 -C 10 X is Cl or Br.

[0051] Furthermore, R 8 , R 9 , R 10 C 6 -C 10 X is Br.

[0052] According to the present invention, based on the total molar amount of the cationic salt groups, the content of the structure represented by formula (1) or the structure represented by formula (2) is independently 40-90 mol%, and the content of the structure represented by formula (3) is 10-60 mol%.

[0053] In the present invention, when the contents of the structure represented by formula (1), the structure represented by formula (2) and the structure represented by formula (3) in the cationic salt group meet the above range, the copolymer can have more efficient and broader antibacterial properties, and the coating containing the copolymer can have a strong and lasting antibacterial and antifouling effect.

[0054] Furthermore, based on the total molar amount of the cationic salt groups, the content of the structure represented by formula (1) or the structure represented by formula (2) is independently 50-80 mol%, and the content of the structure represented by formula (3) is 20-50 mol%.

[0055] According to the present invention, based on the total molar amount of the copolymer, the content of the reactive functional groups is 2-20 mol%.

[0056] In the present invention, the copolymer contains a relatively high content of reactive functional groups, and the copolymer can be used in combination with a coating resin, wherein the coating resin includes a polyester resin, a polyurethane resin, a polyacrylic resin, an epoxy resin, an alkyd resin, an amino resin, etc., and solidifies the adhesive as a coating filling component, so that the copolymer can impart a long-lasting antibacterial property to the coating material while significantly improving the bonding property between the coating material and the substrate, making the coating more durable.

[0057] Furthermore, based on the total molar amount of the copolymer, the content of the reactive functional groups is 5-15 mol%.

[0058] According to the present invention, the reactive functional groups are amino, hydroxyl and amide groups, which are applicable to the curing systems of polyester resins, polyurethane resins, polyacrylic resins, epoxy resins, alkyd resins and amino resins.

[0059] According to the present invention, the copolymer comprises at least three branched chains.

[0060] In the present invention, the copolymer comprising at least three branches refers to a star-shaped copolymer with at least three branches radiating from a central point.

[0061] In the present invention, the copolymer has excellent water solubility, can form a stable aqueous dispersion, and can replace the surfactant of water-based resin or water-based coating. Specifically, in the present invention, the solution viscosity of the aqueous solution of the copolymer with a mass concentration of 10wt% at room temperature is 2-50cp, preferably 5-30cp; the solution viscosity of the aqueous solution of the copolymer with a mass concentration of 15wt% at room temperature is 10-100cp, preferably 20-80cp.

[0062] The second aspect of the present invention provides a method for preparing a reactive branched isobutylene-based composite cationic salt copolymer, characterized in that the preparation method comprises:

[0063] (1) contacting and mixing an initiator solution and a monomer solution in a microchannel reactor under cationic polymerization conditions to perform a cationic polymerization reaction to obtain a solution containing a branched isobutylene-alkylstyrene copolymer;

[0064] (2) contacting the solution of the branched isobutylene-alkylstyrene copolymer with a halogen to carry out a halogenation reaction to obtain a solution containing a halogenated branched isobutylene-based copolymer;

[0065] (3) adding a phosphine compound to the solution of the halogenated branched isobutylene-based copolymer to carry out a first ionization reaction, and then adding a nitrogen compound to carry out a second ionization reaction to obtain a solution containing a branched isobutylene-based composite cationic salt copolymer;

[0066] (4) adding a compound having an active functional group to the solution of the branched isobutylene-based composite cationic salt copolymer to carry out an active functionalization reaction to obtain the reactive branched isobutylene-based composite cationic salt copolymer;

[0067] The initiator solution comprises at least one multifunctional initiator, at least one activator, at least one co-initiator and at least one halogenated alkane.

[0068] In the present invention, in the preparation method of the reactive branched isobutylene-based composite cationic salt copolymer, in the presence of a multifunctional initiator, a cationic polymerization reaction of isobutylene and alkylstyrene is carried out in a microchannel reactor to obtain an isobutylene-alkylstyrene copolymer with a branched structure, and a reactive branched isobutylene-based composite cationic salt copolymer is obtained through a halogenation reaction, an ionization reaction and an active functionalization reaction. The copolymer has a star-shaped branched structure including a plurality of branches, and the branched structure simultaneously carries a composite cationic salt group and a reactive functional group, so that the copolymer has excellent antibacterial properties and cross-linking and curing capabilities, can be used and co-cross-linked and cured with polyester resins, polyurethane resins, polyacrylic resins, epoxy resins, alkyd resins and amino resins, and can significantly improve the bonding properties between the coating material and the surface of the substrate while giving the coating material excellent antibacterial properties, and is widely applicable to substrates, including plastics, glass, metals, ceramics, wood, concrete and the like.

[0069] Cationic polymerization

[0070] According to the present invention, the molar ratio of the multifunctional initiator, the activator and the co-initiator is 1:0.2-1.5:3-15.

[0071] Furthermore, the molar ratio of the multifunctional initiator, the activator and the co-initiator is 1:0.5-1.2:5-10.

[0072] According to the present invention, the multifunctional initiator is an organic compound containing at least three functional groups having cationic initiation reaction activity.

[0073] In the present invention, the multifunctional initiator includes but is not limited to trifunctional, tetrafunctional, pentafunctional, hexafunctional, heptafunctional, and octafunctional initiators, such as 1,3,5-tribenzyl chloride, 1,3,5-tribenzyl bromide, 1,3,5-tricumyl chloride, 1,3,5-tricumyl bromide, 1,3,5-tricumyl alcohol, 3,5,3',5'-biphenyltetrabenzyl chloride, 3,5,3',5'-biphenyltetrabenzyl bromide, 3,5,3',5'-biphenyltetracumyl chloride, 3,5,3',5'-biphenyltetracumyl bromide, and 3,5,3',5'-biphenyltetracumyl alcohol. The trifunctional initiator 1,3,5-tricumyl chloride is preferred in the present invention.

[0074] In the present invention, the co-initiator refers to Lewis acid commonly used in cationic polymerization, including but not limited to ALCL 3 , EtALCL 2 , Et 2 ALCL, TiCL 4 SnCL 4 、ZnCL 2 , BCL3 , BBr 3 EtALCL is preferred in the present invention 2 .

[0075] In the present invention, the activator refers to a substance that can improve the polymerization activity of the cationic active center. The activator used in the present invention is tetrachlorobenzoquinone (tetrachlorobenzoquinone).

[0076] According to the present invention, the monomer solution comprises isobutylene monomer, alkylstyrene monomer, at least one alkane, at least one halogenated alkane and optionally at least one molecular weight regulator.

[0077] In the present invention, based on the total molar amount of the isobutylene monomer and the alkylstyrene monomer, the amount of the isobutylene monomer is 55-80 mol%, preferably 60-75 mol%; the amount of the alkylstyrene monomer is 20-45 mol%, preferably 25-40 mol%.

[0078] In the present invention, the mixed solvent composed of at least one alkane and at least one halogenated alkane in the monomer solution is used as the solvent system, which can take into account the solubility of different polar units in the copolymer including isobutylene units and alkylstyrene units, and can provide a good dissolution effect for the copolymer prepared by the present invention.

[0079] In the present invention, the alkane is a conventional C 5 -C 8 Straight chain alkanes and / or C 5 -C 6 Cyclic alkanes include, but are not limited to, n-pentane, n-hexane, n-heptane, n-octane, n-heptane, cyclopentane, and cyclohexane. Preferably, in order to obtain a particularly efficient and highly selective halogenation reaction, linear or cyclic alkanes with a purity of ≥99.5% are preferred, such as n-hexane or cyclohexane with a purity of ≥99.5%.

[0080] In the present invention, the halogenated alkane is a conventional C 1 -C 4 The halogenated alkanes include but are not limited to monofluoromethane, difluoromethane, trifluoromethane, carbon tetrafluoride, monofluoroethane, difluoroethane, trifluoroethane, tetrafluoroethane, pentafluoroethane, hexafluoroethane, monofluoropropane, difluoropropane, trifluoropropane, tetrafluoropropane, monofluorobutane, difluorobutane, trifluorobutane, tetrafluorobutane, monochloromethane, dichloromethane, trichloromethane, carbon tetrachloride, monochloroethane, dichloroethane, trichloroethane, tetrachloroethane, monochloropropane, dichloropropane, trichloropropane, tetrachloropropane, and monochlorobutane. Preferably, in order to meet the temperature conditions of different chemical reactions, the halogenated alkanes are selected from dichloromethane and / or carbon tetrachloride.

[0081] According to the present invention, based on the total volume of the alkane and the halogenated alkane, the volume percentage of the alkane is 30-70 vol%.

[0082] In the present invention, when the volume percentage of the alkane in the mixed solvent is controlled to meet the above range, a good dissolving effect can be provided for the copolymer prepared in the present invention.

[0083] Furthermore, based on the total volume of the alkane and the halogenated alkane, the volume percentage of the alkane is 40-60 vol%.

[0084] According to the present invention, the mass concentration of the monomer solution is 5-50%, preferably 10-40%, and more preferably 10-30%.

[0085] In the present invention, the molecular weight regulator refers to a comonomer that can regulate the molecular weight of the copolymer without introducing other structures. Suitable molecular weight regulators include but are not limited to diisobutylene and / or m-methylstyrene.

[0086] According to the present invention, based on the total molar amount of the isobutylene monomer and the alkylstyrene monomer, the amount of the molecular weight regulator is 0.5 mol%-5 mol%.

[0087] In the present invention, when the amount of the molecular weight regulator is controlled to meet the above range, the molecular weight and molecular weight distribution of the copolymer can be more stably controlled, and in particular, a copolymer with a lower weight average molecular weight and a narrower molecular weight distribution can be obtained.

[0088] Furthermore, based on the total molar amount of the isobutylene monomer and the alkylstyrene monomer, the amount of the molecular weight regulator is 1 mol%-4 mol%.

[0089] According to the present invention, the conditions of the cationic polymerization reaction include: reaction time of 3-30 min; reaction temperature of -40°C to 0°C.

[0090] Furthermore, the conditions of the cationic polymerization reaction include: reaction time of 5-20 min; reaction temperature of -30°C to -10°C.

[0091] In the present invention, the reaction time of the cationic polymerization reaction includes the sum of the microchannel residence time and the tubular reactor residence time.

[0092] In the present invention, the reaction time (ie, residence time) of the polymerization reaction in the microchannel is controlled by adjusting the material flow rate, and the material flow rate is generally controlled to be 3-10 mL / min.

[0093] According to the present invention, preferably, before the cationic polymerization reaction, the initiator solution and the monomer solution are each independently subjected to a precooling treatment. In the present invention, there is no limitation on the temperature of the precooling treatment, for example, the initiator solution and the monomer solution are subjected to a precooling treatment so that the temperature of the initiator solution and the monomer solution is precooled and controlled to a set reaction temperature, or close to the set reaction temperature.

[0094] According to the present invention, the weight average molecular weight Mw of the branched isobutylene-based copolymer is 2×10 3 g / mol-2×10 4 g / mol, and the molecular weight distribution coefficient Mw / Mn is 1.5-2.5.

[0095] Furthermore, the weight average molecular weight Mw of the branched isobutylene-based copolymer is 5×10 3 g / mol-1.5×10 4 g / mol, and the molecular weight distribution coefficient Mw / Mn is 1.6-2.2.

[0096] In the present invention, the microchannel reactor generally has 5-10 reaction modules, at least one module is used to precool the initiator solution logistics 1, at least one module is used to precool the monomer solution logistics 2, at least one module is used to contact and mix the initiator solution logistics 1 and the monomer solution logistics 2, and the remaining modules are used for polymerization reaction.

[0097] In the present invention, the microchannel reactor refers to a channel reactor with a space size generally between 0.2 and 3 mm. There is no particular limitation on the channel form of the microchannel reaction, including but not limited to broken line, wave, arc, star, and heart shapes.

[0098] In the present invention, the monomer solution and the initiator solution are pre-cooled, contact-mixed and rapidly polymerized in the microchannel reaction, and then flow out of the microchannel reactor into the tubular reactor to further promote the later reaction, so that the polymerization reaction is completed and the total reaction time (residence time) is controlled to be at least 15 minutes.

[0099] In the present invention, preferably, the tubular reactor is a coil reactor to ensure sufficient residence time for the reaction to proceed completely.

[0100] In the present invention, the material flowing out of the tubular reactor enters a neutralization and water washing reactor. The neutralization and water washing reactor is filled with deionized water of a volume almost equal to the total amount of the reaction material, and the metal ions in the material are washed away while eliminating the reaction activity. After the material is received, the stirring is stopped and the layers are separated, and the aqueous solution of the lower layer is separated to obtain a solution containing the branched isobutylene copolymer.

[0101] In a specific embodiment of the present invention, Figure 1 As shown, the cationic polymerization reaction is carried out according to the following steps:

[0102] (1) Stream 1 is an initiator solution, comprising at least one multifunctional initiator, at least one activator, at least one co-initiator, and at least one halogenated alkane as a solvent;

[0103] (2) Stream 2 is a monomer solution comprising isobutylene monomer, alkylstyrene monomer, at least one alkane, at least one halogenated alkane and optionally at least one molecular weight regulator;

[0104] (3) Stream 1 and Stream 2 are respectively fed into the microchannel reactor in a continuous flow by a feed pump, and are respectively pre-cooled by the reaction module 4-1 and the reaction module 4-2, and then mixed and contacted in the reaction module 4-3, and polymerization reactions are carried out in the reaction modules 4-4 to 4-10;

[0105] (4) the material flowing out of the microchannel reactor enters the tubular reactor to continue the cationic polymerization reaction;

[0106] (5) The completely reacted material flowing out of the tubular reactor enters a water washing kettle with a mechanical stirrer, which is filled with deionized water of a volume almost equal to that of the reaction material, and the metal ions in the material are removed while terminating the initiator system. After all the material has been received, the material is allowed to stand still and the lower layer of the aqueous solution is separated to obtain a solution containing the branched isobutylene copolymer.

[0107] Halogenation reaction

[0108] In the present invention, the halogenation reaction of the branched isobutylene-based copolymer is carried out in a dark box protected from light.

[0109] According to the present invention, based on the molar content of the structural unit of alkylstyrene, the molar ratio of the branched isobutylene-alkylstyrene copolymer to the halogen is 1:0.4-1.2, preferably 1:0.5-1.

[0110] According to the present invention, the halogenation reaction is carried out under the irradiation of visible light.

[0111] In the present invention, the light source of the visible light is a monochromatic wavelength LED light source, specifically, the wavelength of the visible light is 590-630nm, and the light emission mode of the visible light is pulsed light emission. Preferably, the pulse time of the pulsed light emission is 5-40s, preferably 10-30s.

[0112] In a specific embodiment of the present invention, the halogenation reaction is carried out according to the following steps:

[0113] The solution containing the branched isobutylene copolymer is injected into a glass reactor with mechanical stirring (with an exhaust pipe on the top of the reactor), and then an acid gas absorbent such as sodium bicarbonate is added in an amount of about 1.1-1.2 times the molar amount of the halogen; the halogen is added to a halogenated alkane solvent to prepare a solution of a certain concentration, such as a carbon tetrachloride solution with a mass concentration of 10%-20%, and is continuously fed into the reactor through a micro-feed pump for halogenation reaction;

[0114] After the halogenation reaction is completed, the reactor is removed from the dark box, and the halogenated copolymer solution is injected into a filter to filter out the solid salt insoluble matter. The filtrate is further centrifuged to remove impurities and then fed into a thin film evaporator through a feed pump to remove low-boiling halogenated alkanes (mainly from the mixed solvent of the cationic polymerization reaction), such as dichloromethane, to obtain a concentrated halogenated branched isobutylene copolymer solution;

[0115] Determine the concentration of the halogenated copolymer solution and the total bromine content of the product, add a high-boiling-point halogenated alkane, such as carbon tetrachloride, and adjust the gel concentration to a certain level, such as 10% by mass, in preparation for the next step of functional modification.

[0116] In the present invention, the feed flow rate of the micro-feed pump is 0.2-2 mL / min, and the temperature of the halogenation reaction is room temperature.

[0117] In a specific embodiment of the present invention, the halogen is liquid bromine.

[0118] Functional modification reaction

[0119] In the present invention, the functional modification reaction refers to the modification of the active halogen groups in the halogenated branched isobutylene copolymer, including cationic saltization and reactive functionalization.

[0120] According to the present invention, the total molar amount of the phosphine compound, the nitrogen compound and the compound with an active functional group is 1.1-1.2 times the molar amount of the halogen.

[0121] In the present invention, when the total molar amount of the phosphine compound, the nitrogen compound and the compound with active functional groups is controlled to meet the above range, it can be ensured that all active halogen groups in the halogenated branched isobutylene-based copolymer are functionalized.

[0122] Specifically, the molar amount of the phosphine compound is 0.1-0.5 times the molar amount of the halogen; the molar amount of the nitrogen compound is 0.3-0.7 times the molar amount of the halogen; and the molar amount of the compound with an active functional group is 0.2-0.4 times the molar amount of the halogen.

[0123] According to the present invention, the nitrogen compound has a structure shown in Formula II or Formula III;

[0124]

[0125] Among them, R 1 , R 2 , R 3 Each independently is C 1 -C 20 Straight chain alkyl, C 1 -C 20 Branched alkyl; R 4 , R 5 , R 6 , R 7 are independently hydrogen, a halogen atom, C 1 -C 10 Straight chain alkyl, C 1 -C 10 Branched chain alkyl, hydroxyl, and nitro groups.

[0126] Furthermore, R 1 , R 2 , R 3 are each independently methyl, C 8 -C 16 of a straight chain alkyl group.

[0127] Furthermore, R 4 For hydrogen, C 1 -C 10 The straight chain alkyl group, R 5 , R 6 , R 7 are independently hydrogen, C 1 -C 5 Straight chain alkyl, C 1 -C 5 Branched chain alkyl, hydroxyl, and nitro groups.

[0128] In the present invention, the nitrogen compound represented by formula II includes but is not limited to trimethylamine, triethylamine, tripropylamine, tributylamine, tripentylamine, trihexylamine, triheptylamine, trioctylamine, trinonylamine, tridecylamine, triundecylamine, tridodecylamine, tridodecylamine, tritridecylamine, tritetradecylamine, tripentadecylamine, trihexadecylamine, triheptadecylamine, trioctadecylamine, trinonadecylamine, trieicosylamine, triphenylamine, N,N-dimethylethylamine, N,N-dimethylpropylamine, N,N-dimethylbutylamine, N,N-dimethylpentylamine amine, 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 compound of formula I is N,N-dimethylalkylamine, especially N,N-dimethylC 8 -C 16 Alkylamines, such as N,N-dimethyldecanylamine, N,N-dimethyldodecylamine and N,N-dimethyltetradecylamine.

[0129] In the present invention, the nitrogen compound represented by formula III includes but is not limited to imidazole, 1-methylimidazole, 1-ethylimidazole, 1-propylimidazole, 1-butylimidazole, 1-pentylimidazole, 1-hexylimidazole, 1-heptylimidazole, 1-octylimidazole, 1-nonylimidazole, 1-decylimidazole, 1-undecylimidazole, 1-dodecylimidazole, 1-tridecylimidazole, 1-tetradecylimidazole, 1-pentadecylimidazole, 1-hexadecylimidazole, 1-heptadecylimidazole, 1-octadecylimidazole, 1,2-dimethylimidazole, 1,2-diethylimidazole, 1,2-dipropylimidazole, 1,2-dibutylimidazole, 1-methyl-2-ethylimidazole, 1-methyl-2-propylimidazole, 1-methyl-2-butylimidazole, 2-methylimidazole, 2-ethylimidazole, 2-propylimidazole, 2-butylimidazole, imidazole, 2-pentylimidazole, 2-hexylimidazole, 2-heptylimidazole, 2-octylimidazole, 2-nonylimidazole, 2-decylimidazole, 2-nitroimidazole, 4-nitroimidazole, 5-nitroimidazole, 1-methyl-4-nitroimidazole, 1-methyl-5-nitroimidazole, 1-ethyl-4-nitroimidazole, 1-ethyl-5-nitroimidazole, 1-propyl-4-nitroimidazole, 1-propyl-5-nitroimidazole At least one of imidazole, 1-butyl-4-nitroimidazole, 1-butyl-5-nitroimidazole, 2-methyl-5-nitroimidazole, 1-butyl-2-methyl-4-nitroimidazole, 1,2-dimethyl-5-nitroimidazole, 2-chloro-4-nitroimidazole, 2-chloro-5-nitroimidazole, and 2-ethyl-4-methylimidazole; imidazole and 1-alkylimidazole (N-alkylimidazole) are preferred in the present invention.

[0130] According to the present invention, the phosphine compound has a structure shown in Formula IV;

[0131]

[0132] Among them, R 8 , R 9 , R 10 Each independently is C 1 -C 10 Straight chain alkyl, C 1 -C 10 Branched alkyl, C 3 -C 10 Cycloalkyl or C 6 -C 10 The aromatic group.

[0133] Furthermore, R 8 , R 9 , R 10 Each independently is C 1 -C 5 Straight chain alkyl, C 1 -C 5 A branched alkyl group, a cycloalkyl group or a phenyl group.

[0134] In the present invention, the phosphine compound represented by formula IV includes but is not limited to trimethyl phosphine, triethyl phosphine, tripropyl phosphine, tributyl phosphine, tripentyl phosphine, tricyclopentyl phosphine, triphenyl phosphine, dimethyl phenyl phosphine, dimethyl ethyl phosphine, dimethyl propyl phosphine, dimethyl butyl phosphine, dimethyl pentyl phosphine, methyl ethyl phenyl phosphine, methyl ethyl propyl phosphine, methyl ethyl butyl phosphine, methyl ethyl pentyl phosphine, methyl ethyl phenyl phosphine, diethyl phenyl phosphine, diethyl methyl phosphine, diethyl propyl phosphine, diethyl butyl phosphine, diethyl pentyl phosphine, The present invention is preferably selected from the group consisting of triphenylphosphine, ethylpropylphenylphosphine, ethylpropylbutylphosphine, ethylpropylpentylphosphine, dipropylphenylphosphine, dipropylmethylphosphine, dipropylethylphosphine, dipropylbutylphosphine, dipropylpentylphosphine, propylbutylphenylphosphine, propylbutylpentylphosphine, dibutylphenylphosphine, dibutylmethylphosphine, dibutylethylphosphine, dibutylpropylphosphine, dibutylpentylphosphine, dipentylphenylphosphine, dipentylmethylphosphine, dipentylethylphosphine, dipentylpropylphosphine and dipentylbutylphosphine; triphenylphosphine is preferred in the present invention.

[0135] According to the present invention, the compound with active functional groups is a nitrogen-containing compound with at least two or more valences, and is preferably selected from at least one of a polyamine compound, a polyol amine compound and a polyamide compound.

[0136] In the present invention, the polyamine compound includes but is not limited to ethylenediamine, propylenediamine, butylenediamine, pentanediamine, hexamethylenediamine, heptanediamine, octanediamine, nonanediamine, decanediamine, undecamethylenediamine, dodecamethylenediamine, meta-xylenediamine, diethylenetriamine, diethylaminopropylamine, triethylenetetramine, tetraethylenepentamine, and the like.

[0137] In the present invention, the polyhydroxyamine compound includes but is not limited to ethanolamine, diethanolamine, triethanolamine, propanolamine, dipropanolamine, tripropanolamine, butanolamine, dibutanolamine, tributanolamine, pentanolamine, dipentanolamine, tripentanolamine and the like.

[0138] In the present invention, the polyamide compound includes but is not limited to oxalyl diamine, malonyl diamine, succinyl diamine, glutaryl diamine, adipic diamine, pimelic diamine, suberyl diamine, azelaic diamine, sebacic diamine and the like.

[0139] In the present invention, a phosphine compound and a nitrogen compound are sequentially added to a solution of the halogenated branched isobutylene-based copolymer to carry out a first ionization reaction and a second ionization reaction, respectively, thereby ensuring that the production process is feasible and controllable, and making the prepared cationic salt copolymer have a broader spectrum of antibacterial properties.

[0140] According to the present invention, the conditions of the first ionization reaction include: reaction temperature of 70-90° C., and reaction time of 4-6 h.

[0141] According to the present invention, the reaction conditions of the second ionization reaction include: reaction temperature of 50-70° C., and reaction time of 4-6 h.

[0142] According to the present invention, in step (4), the conditions of the activation reaction include: reaction temperature of 40-70° C., and reaction time of 3-5 h.

[0143] In one embodiment of the present invention, the functionalization reaction is carried out according to the following steps:

[0144] (i) injecting a certain concentration of halogenated branched isobutylene copolymer solution into a multifunctional stirred reactor with jacket heating and top reflux, first adding a set amount of phosphine compound, the amount of which is set according to the total halogen content, stirring and heating to 70-90° C. and maintaining reflux reaction for 4-6 hours, and the reaction system gradually changes from a solution state to a slurry state;

[0145] (ii) After the reaction is completed, the temperature of the reactor is adjusted to 50-70° C., a set amount of nitrogen compound is added, and the amount added is set according to the total halogen content, and the slurry reaction is continued for 4-6 hours;

[0146] (iii) After the reaction is completed, the temperature of the reactor is adjusted to 40-70° C. again, and a set amount of a compound with an active functional group is added, the amount of which is set according to the total halogen content, and the slurry reaction is continued for 3-5 hours;

[0147] (iv) After the reaction is completed, the slurry material is placed in a filter to separate the solvent, and the filtered copolymer is in the form of fine particles, which are poured into a washing kettle filled with halogenated alkane for stirring and washing, and then separated again by filtering to obtain the reactive branched isobutylene-based composite cationic salt copolymer.

[0148] The third aspect of the present invention provides a reactive branched isobutylene-based composite cationic salt copolymer prepared by the above preparation method.

[0149] In the present invention, the reactive branched isobutylene-based composite cationic salt copolymer can be used to modify coating resins, such as polyester resins, polyurethane resins, polyacrylic resins, epoxy resins, alkyd resins, and amino resins. For example, the reactive branched isobutylene-based composite cationic salt copolymer can be directly added during the synthesis process of the coating resin, and the copolymer can be introduced into the polymer molecular chain of the coating resin in an in-situ manner to achieve modification of the coating resin, impart antibacterial properties to the coating resin, and improve the bonding performance between the coating prepared from the coating resin and the surface of the substrate.

[0150] The fourth aspect of the present invention provides an antibacterial coating, characterized in that the antibacterial coating comprises the above-mentioned reactive branched isobutylene-based composite cationic salt copolymer and a coating resin.

[0151] In the present invention, the coating resin refers to a general-purpose cross-linkable and curable resin used in coatings, including at least one of polyester resin, polyurethane resin, polyacrylic resin, epoxy resin, alkyd resin, and amino resin.

[0152] In the present invention, the reactive branched isobutylene-based composite cationic salt copolymer has active groups that can be cross-linked and cured with general-purpose coating resins, such as amine groups, hydroxyl groups, and amide groups. Active groups suitable for specific coating resin systems or resin curing systems can be selected according to actual needs, and used and co-cured with the resin. While giving the coating material stable and lasting antibacterial properties, the bonding performance between the coating material and the surface of the substrate is improved, making the protective coating more durable and widely applicable to substrates, including plastics, glass, metals, ceramics, wood, concrete, etc.

[0153] In the present invention, unless otherwise specified, the room temperature is 25°C.

[0154] The present invention will be described in detail below through examples.

[0155] The molecular weight and distribution of the branched isobutylene-based copolymer were determined using a LC-20A gel permeation chromatograph (GPC) produced by Shimadzu Corporation of Japan.

[0156] The content of each structural unit in the branched isobutylene-based copolymer and the reactive branched isobutylene-based composite cationic salt copolymer was measured using an AVANCE NEO 600M nuclear magnetic resonance spectrometer produced by Bruker, Switzerland.

[0157] The monomer polymerization conversion of the branched isobutylene-based copolymer was measured by headspace method using Agilent 7890 gas chromatograph.

[0158] The halogen content of the halogenated branched isobutylene-based copolymer was measured using a ZSX Primus 1V X-ray fluorescence spectrometer produced by Rigaku Corporation of Japan.

[0159] The viscosity of the aqueous solution of the reactive branched isobutylene-based complex cationic salt with a content of 10 wt % and 15 wt % was measured using a DV1 type rotary viscometer produced by Brookfield, USA, at 25°C.

[0160] The raw materials used in the examples and comparative examples are all commercially available.

[0161] Example 1

[0162] All reaction experiments were carried out under nitrogen protection.

[0163] (1) Preparation of branched isobutylene-based copolymers

[0164] Initiator solution logistics 1: add 120 mL of refined dichloromethane solvent into a 250 mL two-necked bottle, add 0.0006 mol of initiator tricumyl chloride, 0.0004 mol of activator tetrachlorobenzoquinone, precool to -10°C after dissolving, add 0.003 mol of co-initiator ethylaluminum dichloride, and prepare an initiator solution for use; wherein the molar ratio of initiator, activator and co-initiator is 1:0.66:5.

[0165] Monomer solution logistics 2: Add 500 g of a mixed solvent of refined cyclohexane and refined dichloromethane (50 / 50, V / V) to a 2L two-necked bottle, precool to -10°C, add 1 mol of isobutylene monomer, 0.56 mol of p-methylstyrene monomer, and 0.02 mol of diisobutylene monomer, mix well and set aside; based on the total molar amount of p-methylstyrene monomer and isobutylene monomer, the amount of isobutylene monomer is 65 mol%, and the amount of molecular weight regulator is 1.3 mol%.

[0166] The monomer solution and the initiator solution are respectively fed into the pre-cooling modules 4-1 and 4-2 of the microchannel reactor (the microchannel is heart-shaped) through feed pumps, mixed and contacted in module 4-3, and polymerization reactions are carried out in modules 4-4 to 4-10. The reactor temperature is controlled at -15°C, the flow rate of the initiator solution is set to 1 mL / min, the flow rate of the monomer solution is set to 6 mL / min, the total time for the mixture solution to pass through modules 4-3 to 4-10 is 8.2 min, and the monomer polymerization conversion rate reaches 97.2%.

[0167] The material flowing out of the microchannel reactor 4 enters the tubular reactor 5, and the residence time is about 10 minutes. The reaction temperature is still maintained at -15°C, and the monomer polymerization conversion rate reaches 100%.

[0168] The material flowing out of the tubular reactor enters a 3L water washing kettle 6 filled with 800mL of deionized water for stirring and washing to terminate the initiator system and remove the aluminum ions in the material. After the material is received, the stirring is stopped and the layers are separated. The lower aqueous solution is separated to obtain a colorless and transparent branched isobutylene copolymer solution 8.

[0169] The weight average molecular weight Mw of the branched isobutylene-based copolymer P1 was determined to be 8640 g / mol, and the molecular weight distribution coefficient Mw / Mn was 1.82.

[0170] (2) Bromination reaction of branched isobutylene copolymer

[0171] Preparation of liquid bromine solution: Take 0.49 mol of liquid bromine and add it into 250 mL of carbon tetrachloride and mix well for later use;

[0172] Under stirring conditions, in a dark box, 0.6 mol of sodium bicarbonate was added to a reactor containing a solution of the branched isobutylene copolymer P1. The liquid bromine solution was fed into the reactor by a feed pump, and the feed rate was set to 1 mL / min. The reactor was pulsed with a 150 W light source with a wavelength of 630 nm to carry out the bromination reaction, and the pulse time was 15 s. The molar ratio of p-methylstyrene to liquid bromine in the branched isobutylene copolymer P1 was 1:0.88.

[0173] After the reaction is completed, the reactor is removed from the dark box, the polymer solution is injected into the filter to filter out the solid insoluble matter, and the filtrate is centrifuged to remove impurities again to obtain a slightly yellow brominated branched isobutylene copolymer solution.

[0174] A thin film evaporator was used to remove and recover dichloromethane from the copolymer solution at a recovery temperature of 40° C. to obtain a concentrated solution of brominated branched isobutylene copolymer XP1. The concentration of the concentrated copolymer solution was measured, and carbon tetrachloride solvent was added to adjust the mass concentration of the copolymer solution to 10 wt % for later use.

[0175] The total bromine content of the brominated branched isobutylene-based copolymer XP1 was determined to be 23.6 wt%.

[0176] (3) Functional modification of brominated branched isobutylene copolymers

[0177] Material 1: triphenylphosphine solution: add 0.12 mol triphenylphosphine to 50 mL carbon tetrachloride solvent and dissolve for later use; wherein the molar ratio of triphenylphosphine to bromine is 0.24:1;

[0178] Material 2: Imidazole solution: add 0.22 mol of imidazole to 30 mL of carbon tetrachloride and dissolve for later use; wherein the molar ratio of imidazole to bromine is 0.45:1;

[0179] Material 3: Hexamethylenediamine solution: add 0.20 mol of hexamethylenediamine to 30 mL of carbon tetrachloride and dissolve for later use; wherein the molar ratio of hexamethylenediamine to bromine is 0.41:1;

[0180] Add triphenylphosphine solution to the solution containing brominated branched isobutylene copolymer XP1, raise the temperature to 80°C and keep reflux reaction for 4 hours, the reaction system gradually changes from solution state to slurry state, and cool down to 60°C after the reaction is completed;

[0181] Add imidazole solution to the system after the reaction, continue to keep the slurry state for 5 hours, and cool to 50°C after the reaction;

[0182] The hexamethylenediamine solution was added to the system after the above reaction, and the reaction was continued in a slurry state for 5 hours, and then the reaction was stopped.

[0183] After the materials in the reactor are cooled to room temperature, the materials are discharged, and the granular polymer is separated by a filter. The polymer is then soaked and washed with dichloromethane, and the pure granular polymer is separated by a filter again. The polymer is vacuum dried at 40°C to obtain the reactive branched isobutylene-based composite cationic salt copolymer A1.

[0184] The content of isobutylene structural units in the reactive branched isobutylene-based composite cationic salt copolymer A1, and the content of cationic salt groups and reactive functional groups in the copolymer were measured. The results are shown in Table 1.

[0185] Example 2

[0186] (1) Preparation of branched isobutylene-based copolymers

[0187] Initiator solution stream 1: same as in Example 1;

[0188] Monomer solution logistics 2: Add 500 g of a mixed solvent of refined cyclohexane and refined dichloromethane (60 / 40, V / V) to a 2L single-necked bottle, precool to -10°C, add 1.28 mol of isobutylene monomer, 0.50 mol of p-methylstyrene monomer, and 0.05 mol of m-methylstyrene monomer, mix well and set aside; based on the total molar amount of p-methylstyrene monomer and isobutylene monomer, the amount of isobutylene monomer is 70 mol%, and the amount of molecular weight regulator is 2.7 mol%.

[0189] The rest is the same as step (1) in Example 1.

[0190] The weight average molecular weight Mw of the branched isobutylene-based copolymer P2 was determined to be 6230 g / mol, and the molecular weight distribution coefficient Mw / Mn was 1.95.

[0191] (2) Bromination reaction of branched isobutylene copolymer

[0192] Preparation of liquid bromine solution: Take 0.43 mol of liquid bromine and add it into 250 mL of carbon tetrachloride and mix well for later use;

[0193] The same bromination reaction method as step (2) in Example 1 was used, except that 0.52 mol of sodium bicarbonate was added to the polymer solution, and a 150 W light source with a wavelength of 595 nm was used to pulse the reactor for bromination reaction, and the pulse time was 10 s. The molar ratio of methyl styrene to liquid bromine in the branched isobutylene copolymer P2 was 1:0.78.

[0194] The rest is the same as Example 1.

[0195] The total bromine content of the brominated branched isobutylene-based copolymer XP2 was determined to be 19.7 wt%.

[0196] (3) Functional modification of brominated branched isobutylene copolymers

[0197] The functional modification reaction was carried out in the same manner as step (3) in Example 1, except that

[0198] Material 1: triphenylphosphine solution: add 0.15 mol triphenylphosphine to 50 mL carbon tetrachloride solvent and dissolve for later use; wherein the molar ratio of triphenylphosphine to bromine is 0.35:1;

[0199] Material 2: N,N-dimethyldodecylamine solution: add 0.15 mol N,N-dimethyldodecylamine to 50 mL carbon tetrachloride and dissolve for later use; wherein the molar ratio of N,N-dimethyldodecylamine to bromine is 0.35:1;

[0200] Material 3: Diethanolamine solution: add 0.17 mol of diethanolamine to 30 mL of carbon tetrachloride and dissolve for later use; wherein the molar ratio of diethanolamine to bromine is 0.40:1;

[0201] Add triphenylphosphine solution to the solution containing brominated branched isobutylene copolymer XP2, raise the temperature to 80°C and keep reflux reaction for 5 hours, the reaction system gradually changes from solution state to slurry state, and cool down to 60°C after the reaction is completed;

[0202] Add N,N-dimethyldodecylamine solution to the system after the reaction, and continue to react in a slurry state for 5 hours. After the reaction is completed, keep the temperature at 60°C.

[0203] A diethanolamine solution was added to the system after the above reaction, and the reaction was continued in a slurry state for 5 hours, and then the reaction was stopped.

[0204] Post-treatment was carried out according to the method of Example 1 to obtain reactive branched isobutylene-based composite cationic salt copolymer A2.

[0205] The content of isobutylene structural units in the reactive branched isobutylene-based composite cationic salt copolymer A2 and the content of cationic salt groups and reactive functional groups in the copolymer were measured. The results are shown in Table 1.

[0206] Example 3

[0207] (1) Preparation of branched isobutylene-based copolymers

[0208] Initiator solution logistics 1: add 200 mL of refined dichloromethane solvent into a 500 mL double-necked bottle, add 0.001 mol of initiator tricumyl chloride and 0.0005 mol of activator tetrachlorobenzoquinone, precool to -10°C after dissolving, add 0.008 mol of co-initiator ethylaluminum dichloride, and prepare an initiator solution for use; wherein the molar ratio of initiator, activator and co-initiator is 1:0.5:8.

[0209] Monomer solution logistics 2: Add 600 g of a mixed solvent of refined cyclohexane and refined dichloromethane (50 / 50, V / V) to a 2L two-necked bottle, precool to -10°C, add 1.02 mol of isobutylene monomer, 0.75 mol of p-methylstyrene monomer, and 0.05 mol of diisobutylene monomer, mix well and set aside; based on the total molar amount of p-methylstyrene monomer and isobutylene monomer, the amount of isobutylene monomer is 60 mol%, and the amount of molecular weight regulator is 2.7 mol%.

[0210] The polymerization reaction was completed in the same manner as in Example 1, except that the reaction temperature was controlled at -10°C, and neutralization and water washing were performed to obtain a branched isobutylene-based copolymer solution.

[0211] The weight average molecular weight Mw of the branched isobutylene-based copolymer P3 was determined to be 4910 g / mol, and the molecular weight distribution coefficient Mw / Mn was 1.99.

[0212] (2) Bromination reaction of branched isobutylene copolymer

[0213] Preparation of liquid bromine solution: Take 0.48 mol of liquid bromine and add it into 250 mL of carbon tetrachloride and mix well for later use;

[0214] Under stirring conditions, in a dark box, 0.58 mol of sodium bicarbonate was added to a reactor containing a solution of the branched isobutylene copolymer P3. The liquid bromine solution was fed into the reactor by a feed pump, and the feed rate was set to 1 mL / min. The reactor was pulsed with a 150W light source with a wavelength of 595 nm to carry out the bromination reaction, and the pulse time was 10 s. Among them, the molar ratio of p-methylstyrene to liquid bromine in the branched isobutylene copolymer P3 was 1:0.64.

[0215] After the reaction is completed, the reactor is removed from the dark box, the polymer solution is injected into the filter to filter out the solid insoluble matter, and the filtrate is centrifuged to remove impurities again to obtain a slightly yellow brominated branched isobutylene copolymer solution.

[0216] The dichloromethane in the copolymer solution was removed and recovered by a thin film evaporator to obtain a concentrated solution of the brominated branched isobutylene-based copolymer XP3, and carbon tetrachloride solvent was added to adjust the mass concentration of the copolymer solution to 10 wt % for standby use.

[0217] The total bromine content of the brominated branched isobutylene-based copolymer XP3 was determined to be 19.9 wt%.

[0218] (3) Functional modification of brominated branched isobutylene copolymers

[0219] Material 1: triphenylphosphine solution: add 0.08 mol triphenylphosphine to 50 mL carbon tetrachloride solvent and dissolve for later use; wherein the molar ratio of triphenylphosphine to bromine is 0.17:1;

[0220] Material 2: 1-butylimidazole solution: add 0.30 mol of imidazole to 50 mL of carbon tetrachloride and dissolve for later use; wherein the molar ratio of 1-butylimidazole to bromine is 0.63:1;

[0221] Material 3: Hexamethylenediamine adipamide solution: add 0.15 mol of hexamethylenediamine adipamide to 30 mL of carbon tetrachloride and dissolve for later use; wherein the molar ratio of hexamethylenediamine adipamide to bromine is 0.31:1;

[0222] Add triphenylphosphine solution to the solution containing brominated branched isobutylene copolymer XP3, raise the temperature to 80°C and keep reflux reaction for 4 hours, the reaction system gradually changes from solution state to slurry state, and cool down to 60°C after the reaction is completed;

[0223] Add 1-butylimidazole solution to the system after the reaction, continue to keep the slurry state for 6 hours, and cool to 50°C after the reaction;

[0224] The hexamethylenediamine adipamide solution was added to the system after the reaction, and the reaction was continued in a slurry state for 4 hours, and then the reaction was stopped.

[0225] After the materials in the reactor are cooled to room temperature, the materials are discharged, and the granular polymer is separated by a filter. The polymer is then soaked and washed with dichloromethane, and the pure granular polymer is separated by a filter again. The polymer is vacuum dried at 40°C to obtain the reactive branched isobutylene-based composite cationic salt copolymer A3.

[0226] The content of isobutylene structural units in the reactive branched isobutylene-based composite cationic salt copolymer A3 and the content of cationic salt groups and reactive functional groups in the copolymer were measured. The results are shown in Table 1.

[0227] Example 4

[0228] (1) Preparation of branched isobutylene-based copolymers

[0229] Initiator solution logistics 1: add 200 mL of refined dichloromethane solvent into a 500 mL two-necked bottle, add 0.001 mol of initiator tricumyl chloride and 0.001 mol of activator tetrachlorobenzoquinone, precool to -20°C after dissolving, add 0.006 mol of co-initiator ethylaluminum dichloride, and prepare an initiator solution for use; wherein the molar ratio of initiator, activator and co-initiator is 1:1:6.

[0230] Monomer solution logistics 2: Add 500 g of a mixed solvent of refined cyclohexane and refined dichloromethane (50 / 50, V / V) to a 2L two-necked bottle, precool to -10°C, add 1.22 mol of isobutylene monomer, 0.37 mol of p-methylstyrene monomer, and 0.04 mol of diisobutylene monomer, mix well and set aside; based on the total molar amount of p-methylstyrene monomer and isobutylene monomer, the amount of isobutylene monomer is 78 mol%, and the amount of molecular weight regulator is 2.4 mol%.

[0231] The polymerization reaction was completed by the method of Example 1, except that the reaction temperature was controlled at -20°C, and neutralization and water washing were performed to obtain a branched isobutylene-based copolymer solution.

[0232] The weight average molecular weight Mw of the branched isobutylene-based copolymer P4 was determined to be 14350 g / mol, and the molecular weight distribution coefficient Mw / Mn was 1.78.

[0233] (2) Bromination reaction of branched isobutylene copolymer

[0234] Preparation of liquid bromine solution: Take 0.37 mol of liquid bromine and add it into 200 mL of carbon tetrachloride and mix well for later use;

[0235] Under stirring conditions, in a dark box, 0.44 mol of sodium bicarbonate was added to the reactor containing the solution of the branched isobutylene copolymer P3. The liquid bromine solution was fed into the reactor by a feed pump, and the feed rate was set to 1 mL / min. The reactor was pulsed with a 150W light source with a wavelength of 630 nm for bromination reaction, and the pulse time was 10 s. Among them, the molar ratio of p-methylstyrene to liquid bromine in the branched isobutylene copolymer P4 was 1:1.

[0236] After the reaction is completed, the reactor is removed from the dark box, the polymer solution is injected into the filter to filter out the solid insoluble matter, and the filtrate is centrifuged to remove impurities again to obtain a slightly yellow brominated branched isobutylene copolymer solution.

[0237] The dichloromethane in the copolymer solution was removed and recovered by a thin film evaporator to obtain a concentrated solution of the brominated branched isobutylene-based copolymer XP4, and carbon tetrachloride solvent was added to adjust the mass concentration of the copolymer solution to 10 wt % for standby use.

[0238] The total bromine content of the brominated branched isobutylene-based copolymer XP4 was determined to be 19.8 wt%.

[0239] (3) Functional modification of brominated branched isobutylene copolymers

[0240] Material 1: triphenylphosphine solution: add 0.11 mol triphenylphosphine to 30 mL carbon tetrachloride solvent and dissolve for later use; wherein the molar ratio of triphenylphosphine to bromine is 0.30:1;

[0241] Material 2: N, N-dimethyloctylamine solution: add 0.17 mol N, N-dimethyloctylamine to 30 mL carbon tetrachloride and dissolve for later use; wherein the molar ratio of N, N-dimethyloctylamine to bromine is 0.46:1;

[0242] Material 3: Diethylenetriamine solution: add 0.12 mol of diethylenetriamine to 30 mL of carbon tetrachloride and dissolve for later use; wherein the molar ratio of diethylenetriamine to bromine is 0.32:1;

[0243] Add triphenylphosphine solution to the solution containing brominated branched isobutylene copolymer XP4, raise the temperature to 80°C and keep reflux reaction for 5 hours, the reaction system gradually changes from solution state to slurry state, and cool down to 60°C after the reaction is completed;

[0244] Add N,N-dimethyloctylamine solution to the system after the reaction, continue to keep the slurry state to react for 5 hours, and cool to 50°C after the reaction;

[0245] Add diethylenetriamine solution to the system after the above reaction, continue to react in a slurry state for 4 hours, and then stop the reaction.

[0246] After the materials in the reactor are cooled to room temperature, the materials are discharged, and the granular polymer is separated by a filter. The polymer is then soaked and washed with dichloromethane, and the pure granular polymer is separated by a filter again. The polymer is vacuum dried at 40°C to obtain the reactive branched isobutylene-based composite cationic salt copolymer A4.

[0247] The content of each structural unit in the reactive branched isobutylene-based composite cationic salt copolymer A4 and the content of the cationic salt group and the reactive functional group in the copolymer were measured. The results are shown in Table 1.

[0248] Table 1

[0249]

[0250] 1 Based on the total molar weight of the copolymer

[0251] Table 1 continued

[0252] sample <![CDATA[Structure (1) 2 > <![CDATA[Structure (2) 2 > <![CDATA[Structure (3) 2 > A1 0 64.6％ 35.4％ A2 50.3％ 0 49.7％ A3 0 78.5％ 21.5％ A4 60.7％ 0 39.3％

[0253] 2 Based on the total molar amount of cationic salt groups

[0254] The isobutylene cationic salt copolymer prepared in the example was mixed with water to prepare an aqueous solution with a mass concentration of 10 wt % and an aqueous solution with a mass concentration of 15 wt %. The solution viscosity of the aqueous solution was tested. The results are shown in Table 2.

[0255] Table 2

[0256] sample 10wt% aqueous solution, cp 25wt% aqueous solution, cp A1 12 34 A2 9 25 A3 6 18 A4 23 55

[0257] It can be seen from Table 2 that the reactive branched brominated isobutylene quaternary phosphonium copolymer prepared in the embodiment of the present invention has excellent water solubility and can form a stable aqueous dispersion.

[0258] Illustrative application examples

[0259] In-situ modification of waterborne polyurethane resin by reactive branched isobutylene-based cationic salt polymer

[0260] (1) Add 720 g of polyethylene glycol to a 5 L multifunctional glass reactor equipped with a mechanical stirrer. The reactor is equipped with a thermocouple thermometer, a water separator, vacuum and nitrogen protection; start slow stirring, heat to 120° C. for vacuum dehydration, and cool to 70° C. after no water flows out;

[0261] (2) adding 100 g of reactive branched isobutylene-based composite cationic salt copolymer A2 into a reaction kettle and dissolving it for 1 hour;

[0262] (3) 41.5 g of tetramethylxylylene diisocyanate (TMXDI) was added dropwise to the reactor using a constant pressure dropper, alkane was added dropwise for 1 h, 1 g of catalyst dibutyltin dilaurate was added, and the reaction was stirred at 70 °C for 5 h;

[0263] (4) Sampling and determining the NCO content; when the NCO content is less than 0.1%, adding 1000 g of deionized water to obtain a waterborne polyurethane resin modified by a branched isobutylene-based composite cationic salt copolymer.

[0264] After the reaction was completed, no residual reactive branched isobutylene-based complex cationic salt copolymer was found in the system, indicating that the reactive branched isobutylene-based complex cationic salt copolymer was successfully introduced into the molecular chain of the waterborne polyurethane, achieving in-situ modification of the polyurethane.

[0265] 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. A reactive branched isobutylene-based composite cationic salt copolymer, characterized in that: The copolymer has a star-branched structure including a plurality of branch chains; The branched chain includes an isobutylene structural unit and a structural unit I shown in formula I; R is a C1-C4 alkylene group, Q1 and Q2 are each independently selected from H, a reactive functional group or a cationic salt group, and in the copolymer, Q1 and Q2 are not all H at the same time.

2. The copolymer according to claim 1, wherein Based on the total molar amount of the copolymer, the content of the isobutylene structural unit is 55-80 mol %, preferably 60-75 mol %.

3. The copolymer according to claim 1 or 2, wherein Based on the total molar amount of the copolymer, the content of the cationic salt group is 5-25 mol %, preferably 8-20 mol %.

4. The copolymer according to any one of claims 1 to 3, wherein The cationic salt groups are nitrogen salt groups and phosphonium salt groups; Preferably, the nitrogen salt group has a structure shown in formula (1) or a structure shown in formula (2); Wherein, R1, R2, and R3 are each independently C1-C 20 Straight chain alkyl, C1-C 20 Branched alkyl, C3-C 10 Cycloalkyl or C6-C 10 R4, R5, R6, R7 are each independently hydrogen, halogen, C1-C 10 Straight chain alkyl, C1-C 10 branched alkyl, hydroxyl, nitro; X ​​is Cl or Br; Preferably, the phosphonium salt group has a structure shown in formula (3); Among them, R8, R9, R 10 Each independently is C1-C 10 Straight chain alkyl, C1-C 10 Branched alkyl, C3-C 10 Cycloalkyl or C6-C 10 Aryl; X is Cl or Br; Preferably, based on the total molar amount of the cationic salt group, the content of the structure represented by formula (1) or the structure represented by formula (2) is independently 40-90 mol%, and the content of the structure represented by formula (3) is 10-60 mol%; Preferably, based on the total molar amount of the cationic salt groups, the content of the structure represented by formula (1) or the structure represented by formula (2) is independently 50-80 mol%, and the content of the structure represented by formula (3) is 20-50 mol%.

5. The copolymer according to any one of claims 1 to 4, wherein Based on the total molar amount of the copolymer, the content of the reactive functional groups is 2-20 mol%, preferably 5-15 mol%; Preferably, the reactive functional group is an amino group, a hydroxyl group or an amide group.

6. The copolymer according to any one of claims 1 to 5, wherein The copolymer comprises at least three branch chains.

7. A method for preparing a reactive branched isobutylene-based composite cationic salt copolymer, characterized in that: The preparation method comprises: (1) contacting and mixing an initiator solution and a monomer solution in a microchannel reactor under cationic polymerization conditions to perform a cationic polymerization reaction to obtain a solution containing a branched isobutylene-alkylstyrene copolymer; (2) contacting the solution of the branched isobutylene-alkylstyrene copolymer with a halogen to carry out a halogenation reaction to obtain a solution containing a halogenated branched isobutylene-based copolymer; (3) adding a phosphine compound to the solution of the halogenated branched isobutylene-based copolymer to carry out a first ionization reaction, and then adding a nitrogen compound to carry out a second ionization reaction to obtain a solution containing a branched isobutylene-based composite cationic salt copolymer; (4) adding a compound having an active functional group to the solution of the branched isobutylene-based composite cationic salt copolymer to carry out an active functionalization reaction to obtain the reactive branched isobutylene-based composite cationic salt copolymer; The initiator solution comprises at least one multifunctional initiator, at least one activator, at least one co-initiator and at least one halogenated alkane.

8. The preparation method according to claim 7, wherein: The molar ratio of the multifunctional initiator, the activator and the co-initiator is 1:0.2-1.5:3-15, preferably 1:0.5-1.2:5-10; Preferably, the multifunctional initiator is an organic compound containing at least three functional groups having cationic initiation reaction activity.

9. The preparation method according to claim 7 or 8, wherein: The monomer solution comprises isobutylene monomer, alkylstyrene monomer, at least one alkane, at least one halogenated alkane and optionally at least one molecular weight regulator; Preferably, based on the total volume of the alkane and the halogenated alkane, the volume percentage of the alkane is 30-70 vol%, preferably 40-60 vol%; Preferably, the mass concentration of the monomer solution is 5-50%, preferably 10-30%; Preferably, based on the total molar amount of the isobutylene monomer and the alkylstyrene monomer, the amount of the molecular weight regulator is 0.5 mol%-5 mol%, preferably 1 mol%-4 mol%.

10. The preparation method according to any one of claims 7 to 9, wherein: The alkane is a straight chain or cyclic alkane with a purity of ≥99.5%; Preferably, the halogenated alkane is a C1-C4 halogenated alkane.

11. The preparation method according to any one of claims 7 to 10, wherein: The conditions of the cationic polymerization reaction include: reaction time of 3-30 min, preferably 5-20 min; reaction temperature of -40°C to 0°C, preferably -30°C to -10°C.

12. The preparation method according to any one of claims 7 to 11, wherein: The weight average molecular weight of the branched isobutylene-based copolymer is 2×10 3 g / mol-2×10 4 g / mol, and the molecular weight distribution coefficient Mw / Mn is 1.5-2.5; Preferably, the weight average molecular weight of the branched isobutylene-based copolymer is 5×10 3 g / mol-1.5×10 4 g / mol, and the molecular weight distribution coefficient Mw / Mn is 1.6-2.

2.

13. The preparation method according to any one of claims 7 to 12, wherein: The molar ratio of the branched isobutylene-alkylstyrene copolymer to the halogen is 1:0.4-1.2, preferably 1:0.5-1, based on the molar content of the structural unit of the alkylstyrene; Preferably, the halogenation reaction is carried out under visible light irradiation conditions; Preferably, the wavelength of the visible light is 590-630nm; Preferably, the visible light is emitted in a pulsed manner, and preferably, the pulse time of the pulsed light is 5-40s, preferably 10-30s.

14. The preparation method according to any one of claims 7 to 13, wherein: The total molar amount of the phosphine compound, the nitrogen compound and the compound with an active functional group is 1.1-1.2 times the molar amount of the halogen; Preferably, the nitrogen compound has a structure shown in Formula II or Formula III; Wherein, R1, R2, and R3 are each independently C1-C 20 Straight chain alkyl, C1-C 20 Branched alkyl, C3-C 10 Cycloalkyl or C6-C 10 R4, R5, R6, R7 are each independently hydrogen, halogen, C1-C 10 Straight chain alkyl, C1-C 10 Branched chain alkyl, hydroxyl, nitro; Preferably, the phosphine compound has a structure shown in Formula IV; Among them, R8, R9, R 10 Each independently is C1-C 10 Straight chain alkyl, C1-C 10 Branched alkyl, C3-C 10 Cycloalkyl or C6-C 10 The aromatic group; Preferably, the compound with active functional groups is a nitrogen-containing compound with at least two or more valences, and is preferably selected from at least one of polyamines, polyol amines and polyamides.

15. The preparation method according to any one of claims 7 to 14, wherein: The conditions of the first ionization reaction include: reaction temperature of 70-90°C, reaction time of 4-6h; Preferably, the conditions of the second ionization reaction include: reaction temperature of 50-70°C, reaction time of 4-6h; Preferably, in step (4), the conditions of the active reaction include: reaction temperature of 40-70° C., and reaction time of 3-5 h.

16. A reactive branched isobutylene-based composite cationic salt copolymer prepared by the preparation method according to any one of claims 7 to 15.

17. An antibacterial coating, characterized in that: The antibacterial coating comprises the reactive branched isobutylene-based composite cationic salt copolymer according to any one of claims 1 to 6 and 16 and a coating resin; Preferably, the coating resin is selected from at least one of polyester resin, polyurethane resin, polyacrylic resin, epoxy resin, alkyd resin and amino resin.

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