Cured active branched isobutenyl cationic salt copolymer and preparation method thereof, curable epoxy resin composition and water-resistant mildew-proof coating

Abstract

The invention relates to the field of functional coatings, and discloses a cured active branched isobutenyl cationic salt copolymer and a preparation method thereof, a curable epoxy resin composition and a water-resistant mildew-proof coating. The copolymer has a star-shaped branched structure comprising a plurality of branched chains; each branched chain comprises a structural unit A, a structural unit B, a structural unit C and an optional structural unit D; the structural unit A is from isobutene; the structural unit B is selected from alkyl styrene containing cationic salt groups; the structural unit C is from alkyl styrene containing a curing active functional group; and the structural unit D is from alkyl styrene. The branched chain structure of the copolymer simultaneously contains high-content cationic salt groups and curing active functional groups, so that the copolymer has good compatibility with epoxy resin and can be used together and co-cured with the epoxy resin, the mildew-proof and antibacterial properties of an epoxy resin coating are improved, and the service life of the epoxy resin coating is prolonged. The aging resistance, the cohesiveness and the water resistance of the epoxy resin coating are obviously improved.

Description

Technical Field

[0001] The invention relates to the field of functional coatings, and in particular to a curing active branched isobutylene-based cationic salt copolymer and a preparation method thereof, a curable epoxy resin composition, and a water-resistant and mildew-proof coating. Background Art

[0002] Epoxy resin has strong cohesion because its curing system contains a large number of polar groups such as epoxy bonds, hydroxyl groups, ether bonds, and amine bonds. The material structure is dense, giving it excellent adhesion to metals, wood, glass, concrete, ceramics, etc., and low curing shrinkage. It has excellent corrosion resistance to various media such as acids, alkalis, and salts. It is widely used in environmentally friendly coatings, including water-based coatings, powder coatings, and high-solid coatings, which are the largest application areas of epoxy resin. However, epoxy resin also has some obvious disadvantages, such as relatively large brittleness, poor impact resistance, low peel strength, poor weather resistance, and easy cracking and gradual powdering when used as a topcoat, resulting in a short service life. For this reason, epoxy resin must be modified to a certain extent, among which improving impact strength (improving brittleness) and peel resistance (improving bonding strength) are the main aspects to obtain satisfactory performance requirements, such as using a higher content of polysulfide rubber or nitrile rubber to modify epoxy resin.

[0003] Antibacterial coatings are a type of functional coatings. In recent years, with the improvement of people's awareness of antibacterial, antibacterial materials have been used more and more widely, especially antibacterial coating materials, which have shown a strong development trend and are widely used in crowded places such as food and drug processing industry, hospitals and schools.

[0004] At present, most antibacterial / antifouling coatings use metal ions or metal oxides as antibacterial agents or antifouling toxic materials, such as Ag, Cu / CuO, ZnO, TiO2, organic tin, etc., and are widely used in different coating fields. The bactericidal mechanism of metal ions belongs to diffusion and release to the coating surface to kill bacteria. It is not only necessary to control the release rate of metal ions, but also with the continuous release of metal ions into the environment, the antibacterial properties of the coating continue to decay, and the stability and durability of the antibacterial properties cannot be maintained. Compared with metal antibacterial agents, polymer antibacterial agents have the characteristics of no migration, no release, safety, low toxicity, stable antibacterial properties, high efficiency and durability, making antibacterial coatings safer, more environmentally friendly, green and low-cost.

[0005] The coating material is a low cross-linking density material. The resin in it, as the adhesive of the additive component, gives the coating material certain mechanical properties through cross-linking and curing reaction, thereby forming a tough and adhesive film on the surface of the base layer to play its role. Therefore, the development of coating materials needs to take into account the balance and optimization of various mechanical properties of coating materials. Summary of the invention

[0006] The purpose of the present invention is to overcome the problem that the mechanical properties and mildew and antibacterial properties of epoxy resin coatings in the prior art cannot be satisfied at the same time, and to provide a curing active branched isobutylene-based cationic salt copolymer and a preparation method, a curable epoxy resin composition and a water-resistant mildew and antibacterial coating. The curing active branched isobutylene-based cationic salt copolymer has a star-shaped branched structure including multiple branches, and the branched structure simultaneously carries a high content of cationic salt groups and curing active functional groups, has good compatibility with epoxy resin, can be used and co-cured with epoxy resin, and significantly improves the aging resistance, adhesion and water resistance of the epoxy resin coating while improving the mildew and antibacterial properties of the epoxy resin coating.

[0007] In order to achieve the above-mentioned object, the first aspect of the present invention provides a curing active branched isobutylene-based cationic salt copolymer, wherein the copolymer has a star-branched structure including a plurality of branches;

[0008] The branched chain includes an isobutylene structural unit and a structural unit I shown in formula I;

[0009]

[0010] R is a C1-C4 alkylene group, Q1 and Q2 are each independently selected from H, a curing active functional group or a cationic salt group, and in the copolymer, Q1 and Q2 are not all H at the same time.

[0011] The second aspect of the present invention provides a method for preparing a cured active branched isobutylene cationic salt copolymer, characterized in that the preparation method comprises:

[0012] (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;

[0013] (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;

[0014] (3) adding a phosphine compound and a nitrogen compound to a solution of the halogenated branched isobutylene copolymer to respectively carry out a first ionization reaction and a second ionization reaction to obtain the cured active branched isobutylene cationic salt copolymer;

[0015] The initiator solution comprises at least one multifunctional initiator, at least one activator, at least one co-initiator and at least one halogenated alkane;

[0016] The total molar amount of the phosphine compound and the nitrogen compound is 0.2-0.8 times that of the halogen.

[0017] The third aspect of the present invention provides a curing active branched isobutylene-based cationic salt copolymer prepared by the above preparation method.

[0018] A fourth aspect of the present invention provides a curable epoxy resin composition, wherein the composition comprises component A and component B; the component A and the component B exist independently of each other;

[0019] The component A comprises epoxy resin and the above-mentioned curing active branched isobutylene cationic salt copolymer;

[0020] The component B comprises a curing agent.

[0021] A fifth aspect of the present invention provides a water-resistant and mildew-proof coating, wherein the water-resistant and mildew-proof coating is obtained by curing the above-mentioned curable resin composition.

[0022] Through the above technical scheme, the curing active branched isobutylene cationic salt copolymer and preparation method, curable epoxy resin composition and water-resistant and mildew-proof coating provided by the present invention achieve the following beneficial effects:

[0023] In the present invention, the curing active branched isobutylene-based cationic salt copolymer has a star-shaped branched structure including multiple branches, and the branched structure simultaneously carries a high content of cationic salt groups and curing active functional groups, has good compatibility with epoxy resin, can be used and co-cured with epoxy resin, and significantly improves the aging resistance, adhesion and water resistance of the epoxy resin coating while improving the mildew and antibacterial properties of the epoxy resin coating.

[0024] Furthermore, the curing active branched isobutylene-based cationic salt copolymer of the present invention has a branched polyolefin skeleton that improves the crosslinking density with epoxy resin and the water resistance of the coating, and reduces the brittleness of the epoxy resin; the low molecular weight base polymer and high benzene ring content make it have good compatibility with epoxy resin, the high cationic salt content makes it have good water solubility and water dispersion stability, the high content of curing active groups makes it able to co-cure with epoxy resin coating to improve the bonding strength of internal components, and the high content of composite cationic salt gives the coating material better antibacterial and mildew-proof properties and polar surface adhesion properties. BRIEF DESCRIPTION OF THE DRAWINGS

[0025] Figure 1 This is a simplified diagram of the process for preparing branched isobutylene-based copolymers.

[0026] Description of Reference Numerals

[0027] 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

[0028] 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.

[0029] The first aspect of the present invention provides a curing active branched isobutylene-based cationic salt copolymer, wherein the copolymer has a star-branched structure including a plurality of branches;

[0030] The branched chain includes an isobutylene structural unit and a structural unit I shown in formula I;

[0031]

[0032] R is a C1-C4 alkylene group, Q1 and Q2 are each independently selected from H, a curing active functional group or a cationic salt group, and in the copolymer, Q1 and Q2 are not all H at the same time.

[0033] In the present invention, the curing active branched isobutylene-based cationic salt copolymer has a star-shaped branched structure including multiple branches, and the branched structure simultaneously carries a high content of cationic salt groups and curing active functional groups, has good compatibility with epoxy resin, can be used and co-cured with epoxy resin, and significantly improves the aging resistance, adhesion and water resistance of the epoxy resin coating while improving the mildew and antibacterial properties of the epoxy resin coating.

[0034] In the present invention, the star-shaped branched structure with multiple branches refers to a star-shaped structure with multiple central divergent branches.

[0035] In the present invention, Q1 and Q2 in the copolymer are not all H at the same time, which means that in each macromolecule of the copolymer as a whole, Q1 and Q2 are not all H, but in some segments on the molecular chain of the copolymer, Q1 and Q2 may be H at the same time.

[0036] Furthermore, R is a methylene group or an ethylene group, preferably a methylene group.

[0037] According to the present invention, based on the total molar amount of the copolymer, the content of the isobutylene structural unit is 60-80 mol%.

[0038] In the present invention, the curing active branched isobutylene-based cationic salt copolymer contains a polyolefin skeleton with a branched structure, which improves the crosslinking density and water resistance of the copolymer and the epoxy resin and reduces the brittleness of the epoxy resin.

[0039] The curing active branched isobutylene cationic salt copolymer of the present invention contains a low weight average molecular weight and a high benzene ring content (structural unit I shown in formula I), so that the copolymer has good compatibility with epoxy resin.

[0040] Furthermore, based on the total molar amount of the copolymer, the content of the isobutylene structural unit is 65-75 mol%.

[0041] 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%.

[0042] In the present invention, the curing active branched isobutylene-based cationic salt copolymer contains a high content of cationic salt groups, which can significantly improve the water solubility and water dispersion stability of the copolymer, making the copolymer more suitable for water-based resins and water-based coatings, and can give the coating material containing the copolymer better antibacterial and mildew-proof properties and polar surface adhesion properties.

[0043] Furthermore, based on the total molar amount of the copolymer, the content of the cationic salt group is 10-20 mol%.

[0044] According to the present invention, the cationic salt group includes the structure shown in formula (1) and the structure described in formula (2);

[0045]

[0046] Wherein, R1, R2, and R3 are each independently C1-C 10 Straight chain alkyl, C1-C 10 Branched alkyl, C3-C 10 Cycloalkyl or C6-C 10 R4 is hydrogen, C1-C 20 R5, R6, and R7 are each independently hydrogen, a halogen atom, a C1-C 10 Straight chain alkyl, C1-C 10 branched alkyl, hydroxyl, nitro; X ​​is Cl or Br.

[0047] Furthermore, R1, R2, and R3 are C6-C 10 R4 is hydrogen, C1-C 10 R5, R6, and R7 are each independently hydrogen, a C1-C4 straight-chain alkyl group, or a nitro group; and X is Br.

[0048] Furthermore, R1, R2, and R3 are phenyl groups; R4 is hydrogen or a C1-C4 straight-chain alkyl group; R5, R6, and R7 are each independently hydrogen or nitro; and X is Br.

[0049] 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) is 10-60 mol%, and the content of the structure represented by formula (2) is 40-90 mol%.

[0050] In the present invention, when the contents of the structure represented by formula (1) and the structure represented by formula (2) in the structural unit B meet the above range, the antibacterial range of the copolymer is broader and a more satisfactory antibacterial and antifungal effect can be obtained.

[0051] Furthermore, based on the total molar amount of the cationic salt groups, the content of the structure represented by formula (1) is 20-50 mol%, and the content of the structure represented by formula (2) is 50-80 mol%.

[0052] According to the present invention, based on the total molar amount of the copolymer, the content of the curing active functional groups is 5-25 mol%.

[0053] In the present invention, the curing active branched isobutylene-based cationic salt copolymer contains a relatively high content of curing active groups, so that the copolymer can be co-cured with the epoxy resin coating to improve the bonding strength of the internal components.

[0054] Furthermore, based on the total molar amount of the copolymer, the content of the curing active functional groups is 8-20 mol%.

[0055] In the present invention, the curing active functional group is an active group that can react with an amine curing agent. Preferably, the curing active functional group is a group having an active halogen.

[0056] According to the present invention, the copolymer comprises at least three branched chains.

[0057] 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.

[0058] The second aspect of the present invention provides a method for preparing a cured active branched isobutylene-based cationic salt copolymer, wherein the preparation method comprises:

[0059] (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;

[0060] (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;

[0061] (3) adding a phosphine compound and a nitrogen compound to a solution of the halogenated branched isobutylene copolymer to respectively carry out a first ionization reaction and a second ionization reaction to obtain the cured active branched isobutylene cationic salt copolymer;

[0062] The initiator solution comprises at least one multifunctional initiator, at least one activator, at least one co-initiator and at least one halogenated alkane;

[0063] The total molar amount of the phosphine compound and the nitrogen compound is 0.2-0.8 times that of the halogen.

[0064] In the preparation method of the curing active branched isobutylene-based 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 curing active branched isobutylene-based cationic salt copolymer is obtained by halogenation reaction and ionization reaction, especially by controlling the dosage ratio of the phosphine compound and the nitrogen compound to the halogen in the ionization reaction process. The curing active branched isobutylene-based cationic salt copolymer has a star-shaped branched structure including a plurality of branches, and the branched structure carries a cationic salt group and a curing active functional group at the same time, has good compatibility with epoxy resin, can be used and co-cured with the epoxy resin, and significantly improves the aging resistance, adhesion and water resistance of the epoxy resin coating while improving the mildew and antibacterial properties of the epoxy resin coating.

[0065] Cationic polymerization

[0066] 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.

[0067] Furthermore, the molar ratio of the multifunctional initiator, the activator and the co-initiator is 1:0.5-1.2:5-10.

[0068] According to the present invention, the multifunctional initiator is an organic compound containing at least three functional groups having cationic initiation reaction activity.

[0069] 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.

[0070] In the present invention, the co-initiator refers to Lewis acid commonly used in cationic polymerization reactions, including but not limited to ALCL3, EtALCL2, Et2ALCL, TiCL4, SnCL4, ZnCL2, BCL3, BBr3, etc., and EtALCL2 is preferred in the present invention.

[0071] 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).

[0072] 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.

[0073] 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 60-80 mol%, preferably 65-75 mol%; the amount of the alkylstyrene monomer is 20-40 mol%, preferably 25-35 mol%.

[0074] 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 polymer including isobutylene units and alkylstyrene units, and can provide a good dissolution effect for the copolymer prepared by the present invention.

[0075] In the present invention, the alkane is a conventional C5-C8 straight-chain alkane and / or C5-C6 cyclic alkane used in the art, including but 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, a straight-chain or cyclic alkane with a purity of ≥99.5% is preferred, such as n-hexane or cyclohexane with a purity of ≥99.5%.

[0076] In the present invention, the halogenated alkane is a conventional C1-C4 halogenated alkane used in the art, including but 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 alkane is selected from dichloromethane and / or carbon tetrachloride.

[0077] 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%.

[0078] 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.

[0079] Furthermore, based on the total volume of the alkane and the halogenated alkane, the volume percentage of the alkane is 40-60 vol%.

[0080] According to the present invention, the mass concentration of the monomer solution is 5-50%, preferably 10-40%.

[0081] 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.

[0082] 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%.

[0083] 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 polymer 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.

[0084] Furthermore, based on the total mass of the isobutylene monomer and the alkylstyrene monomer, the amount of the molecular weight regulator is 1 mol%-4 mol%.

[0085] According to the present invention, the conditions of the cationic polymerization reaction include: reaction time of 5-30 minutes; reaction temperature of -40°C to 0°C.

[0086] Furthermore, the conditions of the cationic polymerization reaction include: reaction time of 8-20 min; reaction temperature of -30°C to -10°C.

[0087] 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.

[0088] 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.

[0089] 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.

[0090] 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.

[0091] 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.

[0092] 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.

[0093] In the present invention, the microchannel reactor refers to a channel reactor with a space size generally in the range of 0.2-3 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.

[0094] 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.

[0095] In the present invention, preferably, the tubular reactor is a coil reactor to ensure sufficient residence time for the reaction to proceed completely.

[0096] 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.

[0097] In a specific embodiment of the present invention, Figure 1 As shown, the cationic polymerization reaction is carried out according to the following steps:

[0098] (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;

[0099] (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;

[0100] (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 in reaction module 4-1 and reaction module 4-2, and then mixed and contacted in reaction module 4-3, and polymerization reactions are carried out in reaction modules 4-4 to 4-10;

[0101] (4) the material flowing out of the microchannel reactor enters the tubular reactor to continue the cationic polymerization reaction;

[0102] (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.

[0103] Halogenation reaction

[0104] In the present invention, the halogenation reaction of the branched isobutylene-based copolymer is carried out in a dark box protected from light.

[0105] 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 1:0.5-1.2, preferably 1:0.6-1.

[0106] According to the present invention, the halogenation reaction is carried out under the irradiation of visible light.

[0107] 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 10-15s.

[0108] In a specific embodiment of the present invention, the halogenation reaction is carried out according to the following steps:

[0109] 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;

[0110] 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 point (boiling point ≤ 40° C.) halogenated alkanes (mainly from the mixed solvent of the cationic polymerization reaction), such as dichloromethane, to obtain a concentrated halogenated branched isobutylene copolymer solution;

[0111] 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.

[0112] 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.

[0113] In a specific embodiment of the present invention, the halogen is liquid bromine.

[0114] Cationic salification

[0115] According to the present invention, the total molar amount of the phosphine compound and the nitrogen compound is 0.2-0.8 times, preferably 0.3-0.7 times, the molar amount of the halogen.

[0116] In the present invention, when the total molar amount of the phosphine compound and the nitrogen compound is controlled to meet the above range, the copolymer can simultaneously carry a high content of cationic salt groups and active groups for curing reaction, so as to obtain better antibacterial and antifungal effects and a higher crosslinking density with the resin.

[0117] Specifically, the molar amount of the phosphine compound is 0.1-0.4 times the molar amount of the halogen; the molar amount of the nitrogen compound is 0.1-0.4 times the molar amount of the halogen.

[0118] According to the present invention, the phosphine compound has a structure shown in Formula I;

[0119]

[0120] Wherein, R1, R2, and R3 are each independently C1-C 10 Straight chain alkyl, C1-C 10 Branched alkyl, C3-C 10 Cycloalkyl or C6-C 10 The aromatic group.

[0121] Furthermore, R1, R2, and R3 are C6-C 10 further, R1, R2, and R3 are phenyl.

[0122] In the present invention, the phosphine compound represented by formula I 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.

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

[0124]

[0125] Wherein R4 is hydrogen, C1-C 20 R5, R6, and R7 are each independently hydrogen, a halogen atom, a C1-C 10 Straight chain alkyl, C1-C 10 Branched chain alkyl, hydroxyl, and nitro groups.

[0126] Further, R4 is hydrogen, C1-C 10A straight-chain alkyl group, R5, R6, and R7 are each independently hydrogen, a C1-C4 straight-chain alkyl group, or a nitro group; further, R4 is hydrogen, a C1-C4 straight-chain alkyl group, and R5, R6, and R7 are each independently hydrogen or a nitro group.

[0127] In the present invention, the nitrogen compound represented by formula II 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.

[0128] In a preferred embodiment of the present invention, a phosphine compound and a nitrogen compound are sequentially added to the solution of the branched halogenated isobutylene copolymer to carry out a first ionization reaction and a second ionization reaction, respectively, to ensure that the production process is feasible and controllable.

[0129] 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.

[0130] 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.

[0131] In one embodiment of the present invention, the functionalization reaction is carried out according to the following steps:

[0132] (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;

[0133] (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;

[0134] (iii) 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 solidified active branched isobutylene cationic salt copolymer.

[0135] The third aspect of the present invention provides a curing active branched isobutylene-based cationic salt copolymer prepared by the above preparation method.

[0136] The fourth aspect of the present invention provides a curable epoxy resin composition, wherein the composition comprises component A and component B; the component A and the component B exist independently;

[0137] The component A comprises epoxy resin and the above-mentioned curing active branched isobutylene cationic salt copolymer;

[0138] The component B comprises a curing agent.

[0139] In the present invention, the curable epoxy resin composition contains the curing active branched isobutylene cationic salt copolymer, and the curing active functional groups contained in the copolymer are co-cured with the epoxy resin through a curing agent, thereby improving the compatibility with the epoxy resin and reducing the brittleness of the epoxy resin coating prepared from the curable resin composition, and improving the mildew and antibacterial properties, aging resistance, adhesion and water resistance of the epoxy resin coating.

[0140] In the present invention, the epoxy resin includes but is not limited to glycidyl epoxy resin and non-glycidyl epoxy resin.

[0141] The glycidyl epoxy resin includes but is not limited to glycidyl ether and glycidyl ester epoxy resins. The glycidyl ether epoxy resins include bisphenol A epoxy resin, linear phenolic epoxy resin, aliphatic glycidyl ether resin, etc.; the glycidyl ester epoxy resin includes diglycidyl phthalate. The non-glycidyl epoxy resin includes but is not limited to alicyclic epoxy resin and epoxidized olefin epoxy resin. The present invention preferably uses a bisphenol A epoxy resin with an epoxy value of 0.1-0.6.

[0142] According to the present invention, the mass ratio of the epoxy resin to the curing active branched isobutylene cationic salt copolymer in the component A is 1:0.1-1.5.

[0143] Furthermore, the mass ratio of the epoxy resin to the curing active branched isobutylene cationic salt copolymer in the component A is 1:0.2-1.

[0144] In the present invention, the curing agent is a divalent or higher polyamine compound suitable for medium and low temperature curing reaction, including but not limited to aliphatic polyamines, aromatic polyamines, dicyandiamide imidazole, modified polyamines, polyamides, etc.

[0145] In the present invention, the amount of the curing agent is such that the total molar amount of active hydrogen (such as active hydrogen on the amine group) in the curing agent is equal to the sum of the molar amount of the epoxy group of the epoxy resin and the molar amount of the curing active group in the branched isobutylene cationic salt copolymer.

[0146] In the present invention, according to the actual use of the curable resin composition, the curable resin composition also includes conventional additives in the art, such as pigments, fillers and various auxiliary agents. The amount of each additive in the composition can also be based on the conventional amount in the art.

[0147] A fifth aspect of the present invention provides a water-resistant and mildew-proof coating, wherein the water-resistant and mildew-proof coating is obtained by curing the above-mentioned curable resin composition.

[0148] In the present invention, the water-resistant and mildew-proof coating has good water-resistant, antibacterial and mildew-proof functions, and is suitable for protective coatings of construction projects in dark and humid environments, such as basements, public baths, bathtubs, food processing workshops in humid environments (breweries, canteens), hospital public health rooms, etc., while effectively inhibiting and preventing the growth and reproduction of bacteria and molds, enhancing the washability of the coating, thereby making the service life of the coating material longer.

[0149] In the present invention, unless otherwise specified, the room temperature is 25°C.

[0150] The present invention will be described in detail below through examples.

[0151] The molecular weight and molecular weight distribution of the branched isobutylene-based copolymer were determined using a LC-20A gel permeation chromatograph (GPC) produced by Shimadzu Corporation of Japan;

[0152] The content of each structural unit in the branched isobutylene-based copolymer and the curing active branched isobutylene-based cationic salt copolymer was measured using an AVANCE NEO 600M nuclear magnetic resonance spectrometer produced by Bruker Company of Switzerland.

[0153] The halogen content of the halogenated branched isobutylene-based copolymer was measured using a ZSX PrimuslV X-ray fluorescence spectrometer produced by Rigaku Corporation of Japan;

[0154] The raw materials used in the examples and comparative examples are all commercially available.

[0155] Example 1

[0156] All reaction experiments were carried out under nitrogen protection.

[0157] (1) Preparation of branched isobutylene-based copolymers

[0158] Initiator solution logistics 1: add 150 mL of refined dichloromethane solvent into a 250 mL double-necked glass bottle, add 0.0007 mol of 1,3,5-tricumyl chloride and 0.0005 mol of tetrachlorobenzoquinone, precool to -10°C after dissolving, add 0.004 mol of ethylaluminum dichloride, and prepare an initiator solution for use, wherein the molar ratio of initiator, activator and co-initiator is 1:0.7:5.7.

[0159] Monomer solution logistics 2: Add 500 g of a mixed solvent of refined cyclohexane and refined dichloromethane (50 / 50, V / V) to a 2L double-necked glass bottle, precool to -10°C, add 1.18 mol of isobutylene monomer, 0.53 mol of p-methylstyrene monomer, and 0.03 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 70 mol%, and the amount of molecular weight regulator is 1.7 mol%.

[0160] 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 -20°C, the flow rate of the initiator solution is set to 0.8 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 8.5 min, and the monomer polymerization conversion rate reaches 96.5%.

[0161] 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 -20°C, and the monomer polymerization conversion rate reaches 100%.

[0162] 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.

[0163] The weight average molecular weight Mw of the branched isobutylene-based copolymer P1 was determined to be 13620 g / mol, and the molecular weight distribution coefficient Mw / Mn was 1.88.

[0164] (2) Bromination reaction of branched isobutylene copolymer

[0165] Preparation of liquid bromine solution: Take 0.53 mol of liquid bromine and add it into 200 mL of carbon tetrachloride and mix well for later use;

[0166] Under stirring conditions, in a dark box, 0.64 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 12 s. The molar ratio of p-methylstyrene to liquid bromine in the branched isobutylene copolymer P1 was 1:1.

[0167] 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.

[0168] The dichloromethane in the copolymer solution was removed and recovered by a thin film evaporator at a recovery temperature of 40° C. to obtain a concentrated solution of the 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.

[0169] The total bromine content of the brominated branched isobutylene-based copolymer XP1 was determined to be 23.9 wt%.

[0170] (3) Cationic saltization of brominated branched isobutylene copolymers

[0171] Material 1: triphenylphosphine solution: add 0.14 mol triphenylphosphine to 50 mL carbon tetrachloride solvent and dissolve for later use; wherein the molar ratio of triphenylphosphine to bromine is 0.26:1;

[0172] Material 2: 1-butylimidazole solution: add 0.15 mol 1-butylimidazole to 30 mL carbon tetrachloride and dissolve for later use; wherein the molar ratio of 1-butylimidazole to bromine is 0.28:1;

[0173] Add triphenylphosphine solution to the solution containing brominated branched isobutylene copolymer XP1, raise the temperature to 80°C and keep reflux reaction for 6 hours, the reaction system gradually changes from solution state to slurry state, and cool down to 60°C after the reaction is completed;

[0174] Add 1-butylimidazole solution to the system after the above reaction, and continue to react in a slurry state for 5 hours;

[0175] After the materials in the reactor are cooled to room temperature, they 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 a cured active branched isobutylene cationic salt copolymer, which is recorded as BBIMS-CA-1.

[0176] The content of each structural unit in the curing active branched isobutylene-based cationic salt copolymer and the content of the cationic salt group in the copolymer were measured. The results are shown in Table 1.

[0177] Example 2

[0178] (1) Preparation of branched isobutylene-based copolymers

[0179] Initiator solution logistics 1: the same as the initiator solution in step (1) of Example 1.

[0180] 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 1.3 mol of isobutylene monomer, 0.5 mol of p-methylstyrene monomer, and 0.1 mol of diisobutylene, mix well and set aside; based on the total molar amount of p-methylstyrene monomer and isobutylene monomer, the amount of isobutylene monomer is 75 mol%, and the amount of molecular weight regulator is 5 mol%.

[0181] The microchannel reactor of Example 1 is still used, except that the reaction temperature is set at -10°C, the flow rate of the initiator solution is 1 mL / min, the flow rate of the monomer solution is 6 mL / min, the total time for the mixture solution to pass through the 4-3 to 4-10 modules is 8.2 min, and the monomer polymerization conversion rate reaches 96.6%.

[0182] 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 -10°C, and the monomer polymerization conversion rate reaches 100%.

[0183] The rest is the same as Example 1.

[0184] The weight average molecular weight Mw of the branched isobutylene-based copolymer P2 was determined to be 4670 g / mol, and the molecular weight distribution coefficient Mw / Mn was 2.13.

[0185] (2) Bromination reaction of branched isobutylene copolymer

[0186] Preparation of liquid bromine solution: Take 0.55 mol of liquid bromine and add it into 250 mL of carbon tetrachloride and mix well for later use;

[0187] The same bromination reaction method as step (2) in Example 1 was used, except that 0.66 mol of sodium bicarbonate was added to the polymer solution, and a 150 W light source with a wavelength of 630 nm was used to pulse the reactor for bromination reaction, and the pulse time was 10 s. The molar ratio of p-methylstyrene to liquid bromine in the branched isobutylene copolymer P2 was 1:1.1.

[0188] The rest is the same as Example 1.

[0189] The total bromine content of the brominated branched isobutylene-based copolymer XP2 was determined to be 22.8 wt%.

[0190] (3) Cationic saltization of brominated branched isobutylene copolymers

[0191] Material 1: triphenylphosphine solution: add 0.1 mol triphenylphosphine to 50 mL carbon tetrachloride solvent and dissolve for later use; wherein the molar ratio of triphenylphosphine to bromine is 0.18:1;

[0192] Material 2: Imidazole solution: add 0.2 mol of imidazole to 50 mL of carbon tetrachloride and dissolve for later use; wherein the molar ratio of imidazole to bromine is 0.36:1;

[0193] Add triphenylphosphine solution to the solution containing brominated branched isobutylene copolymer XP2, 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;

[0194] Add imidazole solution to the product after the above reaction, and continue to react in a slurry state for 5 hours;

[0195] The rest is the same as in Example 1 to obtain a curable active branched isobutylene cationic salt copolymer, which is labeled as BBIMS-CA-2.

[0196] The content of each structural unit in the curing active branched isobutylene-based cationic salt copolymer and the content of the cationic salt group in the copolymer were measured. The results are shown in Table 1.

[0197] Example 3

[0198] (1) Preparation of branched isobutylene-based copolymers

[0199] Initiator solution logistics 1: the same as the initiator solution in step (1) in Example 1.

[0200] Monomer solution stream 2: the same as the monomer solution in step (1) in Example 1.

[0201] The microchannel reactor of Example 1 is still used, except that the reaction temperature is set at -15°C, the flow rate of the initiator solution is 1 mL / min, the flow rate of the monomer solution is 6 mL / min, the total time for the mixture solution to pass through the 4-3 to 4-10 modules is 8.2 min, and the monomer polymerization conversion rate reaches 95.5%.

[0202] 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%.

[0203] The rest is the same as Example 1.

[0204] The weight average molecular weight Mw of the branched isobutylene-based copolymer P3 was determined to be 7370 g / mol, and the molecular weight distribution coefficient Mw / Mn was 2.01.

[0205] (2) Bromination reaction of branched isobutylene copolymer

[0206] Preparation of liquid bromine solution: Take 0.45 mol of liquid bromine and add it into 250 mL of carbon tetrachloride and mix well for later use;

[0207] The same bromination reaction method as step (2) in Example 1 was used, except that 0.54 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 p-methylstyrene to liquid bromine in the branched isobutylene copolymer P3 was 1:0.85.

[0208] The rest is the same as Example 1.

[0209] The total bromine content of the brominated branched isobutylene-based copolymer XP3 was determined to be 19.7 wt%.

[0210] (3) Cationic saltization of brominated branched isobutylene copolymers

[0211] Material 1: triphenylphosphine solution: add 0.1 mol triphenylphosphine to 50 mL carbon tetrachloride solvent and dissolve for later use; wherein the molar ratio of triphenylphosphine to bromine is 0.22:1;

[0212] Material 2: Imidazole solution: add 0.15 mol of imidazole to 50 mL of carbon tetrachloride and dissolve for later use; wherein the molar ratio of imidazole to bromine is 0.33:1;

[0213] The rest of the process was the same as step (3) in Example 2 to obtain a cured active branched isobutylene-based composite cationic salt copolymer, which was labeled as BBIMS-CA-3.

[0214] The content of each structural unit in the curing active branched isobutylene-based cationic salt copolymer and the content of the cationic salt group in the copolymer were measured. The results are shown in Table 1.

[0215] Example 4

[0216] (1) Preparation of branched isobutylene-based copolymers

[0217] Initiator solution logistics 1: add 150 mL of refined dichloromethane solvent, 0.0009 mol of 1,3,5-tricumyl chloride and 0.0007 mol of tetrachlorobenzoquinone to a 250 mL double-necked glass bottle, precool to -10°C after dissolving, add 0.004 mol of ethylaluminum dichloride, and prepare an initiator solution for use; wherein the molar ratio of initiator, activator and co-initiator is 1:0.78:4.4.

[0218] 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 1.2 mol of isobutylene monomer, 0.7 mol of p-methylstyrene monomer, and 0.05 mol of diisobutylene, 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 2.5 mol%.

[0219] The microchannel reactor of Example 1 is still used, except that the reaction temperature is set at -15°C, the flow rate of the initiator solution is 1 mL / min, the flow rate of the monomer solution is 6 mL / min, the total time for the mixture solution to pass through the 4-3 to 4-10 modules is 8.2 min, and the monomer polymerization conversion rate reaches about 96.8%.

[0220] 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%.

[0221] The rest is the same as Example 1.

[0222] The weight average molecular weight Mw of the branched isobutylene-based copolymer P4 was determined to be 9150 g / mol, and the molecular weight distribution coefficient Mw / Mn was 1.98.

[0223] (2) Bromination reaction of branched isobutylene copolymer

[0224] Preparation of liquid bromine solution: Take 0.56 mol of liquid bromine and add it into 250 mL of carbon tetrachloride and mix well for later use;

[0225] The same bromination reaction method as step (2) in Example 1 was used, except that 0.67 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 p-methylstyrene to liquid bromine in the branched isobutylene copolymer P4 was 1:0.8.

[0226] The rest is the same as Example 1.

[0227] The total bromine content of the brominated branched isobutylene-based copolymer XP4 was determined to be 22.1 wt%.

[0228] (3) Cationic saltization of brominated branched isobutylene copolymers

[0229] 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 0.14:1;

[0230] Material 2: Imidazole solution: add 0.3 mol of imidazole to 50 mL of carbon tetrachloride and dissolve for later use; wherein the molar ratio of imidazole to bromine is 0.54:1;

[0231] Add triphenylphosphine solution to the solution containing brominated branched isobutylene copolymer XP4, 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;

[0232] Add imidazole solution to the product after the above reaction, and continue to react in a slurry state for 6 hours;

[0233] The rest is the same as in Example 1 to obtain a curing active branched isobutylene-based composite cationic salt copolymer, which is labeled as BBIMS-CA-4.

[0234] The content of each structural unit in the curing active branched isobutylene-based cationic salt copolymer and the content of the cationic salt group in the copolymer were measured. The results are shown in Table 1.

[0235] Example 5

[0236] (1) Preparation of branched isobutylene-based copolymers

[0237] The same initiator solution, monomer solution and polymerization method as in Example 4 were used.

[0238] The weight average molecular weight Mw of the branched isobutylene-based copolymer P5 was determined to be 9060 g / mol, and the molecular weight distribution coefficient Mw / Mn was 2.01.

[0239] (2) Bromination reaction of branched isobutylene copolymer

[0240] Preparation of liquid bromine solution: Take 0.63 mol of liquid bromine and add it into 250 mL of carbon tetrachloride and mix well for later use;

[0241] The same bromination reaction method as step (2) in Example 1 was used, except that 0.76 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 p-methylstyrene to liquid bromine in the branched isobutylene copolymer P5 was 1:0.9.

[0242] The rest is the same as step (3) in Example 4.

[0243] The total bromine content of the branched brominated isobutylene-based copolymer XP5 was determined to be 22.1 wt%.

[0244] (3) Cationic saltization of brominated branched isobutylene copolymers

[0245] Material 1: triphenylphosphine solution: add 0.15 mol triphenylphosphine to 80 mL carbon tetrachloride solvent and dissolve for later use; wherein the molar ratio of triphenylphosphine to bromine is 0.24:1;

[0246] Material 2: 1-butylimidazole solution: add 0.15 mol 1-butylimidazole to 50 mL carbon tetrachloride and dissolve for later use; wherein the molar ratio of 1-butylimidazole to bromine is 0.24:1;

[0247] Add triphenylphosphine solution to the solution containing branched brominated isobutylene copolymer XP5, 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;

[0248] Add 1-butylimidazole solution to the product after the above reaction, and continue to react in a slurry state for 5 hours;

[0249] The rest is the same as in Example 1 to obtain a curing active branched isobutylene-based composite cationic salt copolymer, which is labeled as BBIMS-CA-5.

[0250] The content of each structural unit in the curing active branched isobutylene-based cationic salt copolymer and the content of the cationic salt group in the copolymer were measured. The results are shown in Table 1.

[0251] Comparative Example 1

[0252] (1) Preparation of branched isobutylene-based copolymers

[0253] Initiator solution stream 1: an initiator solution prepared in the same manner as in Example 1;

[0254] Monomer solution stream 2: a monomer solution prepared in the same manner as in Example 1;

[0255] The same polymerization method as step (1) in Example 1 was adopted.

[0256] The weight average molecular weight Mw of the branched isobutylene-based copolymer DP1 was determined to be 13860 g / mol, and the molecular weight distribution coefficient Mw / Mn was 1.92.

[0257] (2) Bromination reaction of branched isobutylene copolymer

[0258] Preparation of liquid bromine solution: Take 0.32 mol of liquid bromine and add it into 200 mL of carbon tetrachloride and mix well for later use;

[0259] The same bromination reaction method as step (2) in Example 1 was adopted, except that 0.38 mol of sodium bicarbonate was added to the polymer solution, wherein the molar ratio of p-methylstyrene to liquid bromine in the branched isobutylene copolymer DP1 was 1:0.6.

[0260] The rest is the same as step (2) in Example 1.

[0261] The total bromine content of the brominated branched isobutylene-based copolymer DXP1 was determined to be 15.8 wt%.

[0262] (3) Quaternary Phosphonium Saltization of Brominated Branched Isobutylene Copolymers

[0263] Material 1: triphenylphosphine solution: add 0.16 mol triphenylphosphine to 50 mL carbon tetrachloride solvent and dissolve for later use; wherein the molar ratio of triphenylphosphine to bromine is 0.5:1;

[0264] Material 2: 1-butylimidazole solution: add 0.2 mol 1-butylimidazole to 30 mL carbon tetrachloride and dissolve for later use; wherein the molar ratio of 1-butylimidazole to bromine is 0.63:1;

[0265] Add triphenylphosphine solution to the solution containing brominated branched isobutylene copolymer DXP1, raise the temperature to 80°C and keep reflux reaction for 6 hours, the reaction system gradually changes from solution state to slurry state, and cool down to 60°C after the reaction is completed;

[0266] Add 1-butylimidazole solution to the system after the above reaction, and continue to react in a slurry state for 6 hours;

[0267] The rest of the process was the same as in Example 1, and a branched isobutylene-based cationic salt copolymer without curing active groups was obtained, which was recorded as BBIMS-CD-1.

[0268] The content of each structural unit in the branched isobutylene-based cationic salt copolymer without curing active groups was measured, and the results are shown in Table 1.

[0269] Table 1

[0270]

[0271] 1 Based on the total molar weight of the copolymer

[0272] Application example - water-resistant and mildew-proof coating

[0273] The water-resistant and mildew-proof coating was prepared according to the following method. The specific formula is shown in Table 2:

[0274] Preparation of component S1 (resin component): deionized water, epoxy resin, BBIMS of the embodiment and comparative example, toughening agent (dioctyl phthalate), film-forming agent (N160), and defoaming agent are mixed and stirred evenly, and silicon dioxide is added to the mixed liquid in batches under stirring of a high-speed shear disperser, and stirred at high speed for 15 minutes; then barium sulfate and quartz powder are added in batches, and stirred at high speed to make the system into a uniform paste, and finally vacuumed and stirred to remove bubbles for 30 minutes.

[0275] Preparation of component S2 (curing agent component): deionized water, curing agent (triethylenetetramine), accelerator (quaternary mercaptan), film-forming agent (N160), and defoaming agent are mixed and stirred evenly. Silicon dioxide is added to the mixed liquid in batches under the stirring of a high-speed shear dispersant, and stirred at high speed for 15 minutes; then barium sulfate and quartz powder are added in batches, and the system is stirred at high speed to become a uniform paste. Finally, vacuum is evacuated and stirred to remove bubbles for 30 minutes.

[0276] For the solvent, filler and auxiliary components added to both S1 and S2, including deionized water, film former, silicon dioxide, barium sulfate, quartz powder and defoamer, they can be added to components S1 and S2 in appropriate proportions as needed. For example, each component can be added to S1 and S2 in a ratio of 5:1, as long as the resin and curing agent can be mixed, dispersed and prepared. Then, S1 and S2 are mixed to prepare a water-resistant and mildew-proof coating for underwater use.

[0277] Table 2

[0278]

[0279] The mechanical properties and bonding strength of the epoxy resin coating after curing were tested, specifically:

[0280] The mechanical properties test was carried out in accordance with GB / T 2567-2008 “Test Methods for Properties of Resin Castings”. After molding, the materials were cured at room temperature for 7 days, and then the tensile strength, elongation and compressive strength of the materials were tested on a RGM-100 microcomputer-controlled electronic universal testing machine.

[0281] The bonding strength test uses a carbon fiber bonding strength tester (model SHTC-10) to test the positive tensile bonding strength. After a simple surface treatment, a Q345 steel plate specimen the size of A4 paper is coated with a layer of epoxy resin coating with a thickness of about 3mm and cured at room temperature for 7 days for testing.

[0282] The test results are shown in Table 3.

[0283] Table 3

[0284] Tensile strength / MPa Elongation / % Compression strength / MPa Bond strength / MPa Application Example 1 33.2 2.2 52.8 2.7 Application Example 2 31.6 3.7 51.4 2.8 Application Example 3 29.3 6.1 48.9 3.2 Application Example 4 30.9 3.9 50.7 2.9 Application Example 5 27.3 7.7 47.6 3.5 Application Example 6 22.6 14.4 43.3 3.8 Comparative application example 1 35.4 1.1 54.3 2.7 Comparative Application Example 2 18.7 17.5 40.5 3.3

[0285] It can be seen from Table 3 that when an equal amount of BBIMS is used to replace epoxy resin, since the cross-linking curing functional group content of BBIMS is significantly lower than that of epoxy resin, as the amount of BBIMS increases, the tensile strength of the coating gradually decreases, the elongation significantly increases, the bonding strength increases, and the compressive strength gradually decreases, indicating that the BBIMS provided by the present invention has the effect of toughening epoxy resin. The use of BBIMS without curing activity in the comparative example and epoxy resin is only equivalent to the role of a toughening agent, which will cause a greater decrease in tensile strength and compressive strength.

[0286] The coatings prepared in Application Examples 1, 2, 5, 6 and Comparative Application Example 1 were applied to the surface of 20×20×1cm ceramic tiles, and applied twice at an interval of 24 hours, and then cured at room temperature for 7 days. In the summer from June to August, when the bacterial microorganisms are proliferating vigorously, the ceramic tiles were placed in a dark and humid corner of the wall, and watered manually to maintain a certain humidity. The mold growth on the coating surface was observed every half a month and recorded. After 3 months, the tiles were taken out, the surface pollutants were brushed off, and the tiles were placed in an oven at 65°C for 24 hours to observe the changes on the coating surface. The specific observation phenomena are shown in Table 4 below.

[0287] Table 4

[0288] Soaking time Application Example 1 Application Example 2 Application Example 5 Application Example 6 Comparative application example 1 0.5 months No mildew No mildew No mildew No mildew No mildew January No mildew No mildew No mildew No mildew Visible mildew spots 1.5 months No mildew No mildew No mildew No mildew Mildew patches appear February Visible mildew spots No mildew No mildew No mildew Obvious mildew spots 2.5 months Visible mildew spots No mildew No mildew No mildew Obvious mold March Mildew patches appear No mildew No mildew No mildew Severe mold Drying at 65℃ Cracks and peeling There are cracks Intact Intact Cracking and peeling

[0289] It can be seen that the cured active branched isobutylene cationic salt polymer provided by the present invention is used in combination with epoxy resin to prepare water-resistant and mildew-proof coatings, which can significantly improve the aging resistance and mildew resistance of epoxy resin coating materials. It is suitable for food processing, public bathing and other places in humid environments, can effectively inhibit the parasitic reproduction of harmful microorganisms such as mold and bacteria, is resistant to cleaning and washing, and improves the sanitary conditions of the environment.

[0290] 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 curing active branched isobutylene 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 curing active 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 60-80 mol %, preferably 65-75 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 10-20 mol%.

4. The copolymer according to any one of claims 1 to 3, wherein The cationic salt group includes the structure shown in formula (1) and the structure described in formula (2); Wherein, R1, R2, and R3 are each independently C1-C 10 Straight chain alkyl, C1-C 10 Branched alkyl, C3-C 10 Cycloalkyl or C6-C 10 R4 is hydrogen, C1-C 20 R5, R6, and R7 are each independently hydrogen, a halogen atom, a C1-C 10 Straight chain alkyl, C1-C 10 branched alkyl, hydroxyl, nitro; X ​​is Cl or Br; Preferably, based on the total molar amount of the cationic salt groups, the content of the structure represented by formula (1) is 10-60 mol%, and the content of the structure represented by formula (2) is 40-90 mol%; More preferably, based on the total molar amount of the cationic salt groups, the content of the structure represented by formula (1) is 20-50 mol %, and the content of the structure represented by formula (2) is 50-80 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 curing active functional group is 5-25 mol%, preferably 8-20 mol%; Preferably, the curing active functional group is a group having an active halogen.

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 cured active branched isobutylene 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 and a nitrogen compound to a solution of the halogenated branched isobutylene copolymer to respectively carry out a first ionization reaction and a second ionization reaction to obtain the cured active branched isobutylene 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; The total molar amount of the phosphine compound and the nitrogen compound is 0.2-0.8 times that of the halogen.

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 total molar amount of the phosphine compound and the nitrogen compound is 0.3-0.7 times that of the halogen.

10. The preparation method according to any one of claims 7 to 9, 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 content of the isobutylene monomer is 60-80 mol%, preferably 65-75 mol%, and the content of the alkylstyrene monomer is 20-40 mol%, preferably 25-35 mol%; Preferably, based on the total mass 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%.

11. The preparation method according to any one of claims 7 to 10, 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.

12. The preparation method according to any one of claims 7 to 11, wherein: The conditions of the cationic polymerization reaction include: reaction time of 5-30 min, preferably 8-20 min; reaction temperature of -40°C to 0°C, preferably -30°C to -10°C.

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

2.

14. The preparation method according to any one of claims 7 to 13, wherein: The molar ratio of the branched isobutylene-alkylstyrene copolymer to the halogen is 1:0.5-1.2, preferably 1:0.6-1, based on the molar content of the structural unit of the alkylstyrene; Preferably, the halogenation reaction is initiated under the irradiation of visible light; 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.

15. The preparation method according to any one of claims 7 to 14, wherein: The phosphine compound has a structure shown in Formula II; Wherein, R1, R2, and R3 are each independently C1-C 10 Straight chain alkyl, C1-C 10 Branched alkyl, C3-C 10 Cycloalkyl or C6-C 10 The aromatic group; Preferably, the nitrogen compound has a structure shown in Formula III; Wherein R4 is hydrogen, C1-C 20 R5, R6, and R7 are each independently hydrogen, a halogen atom, a C1-C 10 Straight chain alkyl, C1-C 10 Branched chain alkyl, hydroxyl, and nitro groups.

16. The preparation method according to any one of claims 7 to 15, 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., and reaction time of 4-6 h.

17. A cured active branched isobutylene-based cationic salt copolymer prepared by the preparation method according to any one of claims 7 to 16.

18. A curable epoxy resin composition, characterized in that The composition comprises component A and component B; the component A and the component B exist independently of each other; The component A comprises an epoxy resin and a curing active branched isobutylene cationic salt copolymer as described in any one of claims 1 to 6 and 17; The component B comprises a curing agent.

19. The curable resin composition according to claim 18, wherein In terms of mass, the mass ratio of the epoxy resin to the curing active branched isobutylene cationic salt copolymer in component A is 1:0.1-1.5; Preferably, the mass ratio of the epoxy resin to the curing active branched isobutylene cationic salt copolymer in the component A is 1:0.2-1 by mass.

20. The curable resin composition according to claim 18 or 19, wherein The curing agent is a polyamine compound.

21. A water-resistant and mildew-proof coating, characterized in that: The water-resistant and mildew-proof coating is obtained by curing the curable resin composition described in any one of claims 18 to 20.

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