Cured active branched isobutylene quaternary phosphonium salt polymer and preparation method thereof, curable epoxy resin composition and waterproof antifouling coating

Abstract

The invention relates to the field of functional coatings, and discloses a cured active branched isobutylene quaternary phosphonium salt polymer and a preparation method thereof, a curable epoxy resin composition and a waterproof antifouling coating. The polymer 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 from alkyl styrene containing quaternary phosphonium 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 polymer contains quaternary phosphonium salt groups and curing active functional groups at the same time, so that the polymer has good compatibility with epoxy resin and can be used together and co-cured with the epoxy resin, and the anti-fouling performance of an epoxy resin coating is improved, and meanwhile, the aging resistance, cohesiveness and waterproof capacity of the epoxy resin coating are remarkably improved.

Description

Technical Field

[0001] The invention relates to the field of functional coatings, and in particular to a cured active branched isobutylene quaternary phosphonium salt polymer and a preparation method thereof, a curable epoxy resin composition, and a waterproof and antifouling coating. Background Art

[0002] Underwater antifouling coatings, especially for various marine engineering structures in the marine environment, such as offshore oil, natural gas drilling and production equipment, ships, etc., are immersed in seawater all year round, and need to be coated with special antifouling coatings to prevent marine organisms from attaching and fouling, so as to ensure the safety and economy of marine facilities. There are many kinds of fouling organisms living in the ocean, which are very easy to attach and parasitize on underwater equipment and hulls, thus bringing great harm, such as causing the hull to increase weight, reduce speed and increase fuel consumption, or attach to warship sonars, reducing the detection performance of sonars, etc. So far, coating antifouling paint is still a widely used and relatively effective method.

[0003] Traditional underwater antifouling coatings use metal compounds as antifouling agents, and the antifouling coating continuously releases metal ions to form a micro-layer of toxic materials to prevent the larvae of fouling organisms from attaching and breeding. The types of antifouling agents have changed with the development of economic and environmental protection requirements. The lead and mercury compounds used in the early days were banned due to their harm to marine life and human health, and were replaced by copper and zinc compounds with little environmental impact, such as copper powder, cuprous oxide, anhydrous copper sulfate, zinc oxide, and organic metal compounds such as copper pyrithione and zinc pyrithione. Among them, cuprous oxide is the most commonly used toxic material. Cuprous oxide has a good effect on preventing shellfish from attaching, but has a poor effect on preventing plants such as seaweed, so it needs to be used in combination with other toxic materials, such as organic tin toxic materials (triphenyltin hydroxide, triphenyltin chloride, triphenyltin acetate) or tetramethylthiuram disulfide, or organic antifouling agents such as isothiazolinone, s-triazine, trichlorophenylmaleimide, etc. Since these antifouling agents are released into the environment to achieve sterilization or antifouling, not only will the antifouling effect decay over time, but in the long run it will cause pollution to the aquatic environment. For example, copper compounds may precipitate and settle in the bottom mud to form permanent pollution. The copper content in the water of ports and docks has attracted more and more attention. Since the toxicity of organotin polymers has a great impact on the reproduction and survival of shellfish in the ocean, the use of organotin antifouling agents is increasingly restricted. Therefore, the development of new underwater antifouling agents that are safe, harmless, long-lasting and efficient to the environment is the focus of future development.

[0004] At present, the antifouling agent used in underwater antifouling coating materials is mainly cuprous oxide (Cu2O), and the usage amount is generally 30% to 50%, but the antifouling performance is still not satisfactory.

[0005] Small molecule cationic salt antibacterial agents, such as quaternary ammonium salts, are widely used water bactericides and algaecides due to their excellent water solubility and little impact on the water environment. They are commonly used in aquaculture, water purification and other fields. However, quaternary phosphonium salts are generally not used because of their strong bactericidal ability and are harmful to aquatic organisms. Summary of the invention

[0006] The purpose of the present invention is to solve the problem that underwater antifouling coatings in the prior art pollute the water environment due to the release of antifouling toxic materials and that the water solubility of small molecule cationic salt antibacterial agents is too good to affect the performance of underwater coatings, and to provide a curing active branched isobutylene quaternary phosphonium salt polymer and its preparation method, a curable epoxy resin composition, and a waterproof and antifouling coating. The curing active branched isobutylene quaternary phosphonium salt polymer has a star-shaped branched structure including multiple branches, and the branched structure simultaneously carries a quaternary phosphonium salt group and a curing active functional group, has good compatibility with epoxy resin, can be used and co-cured with epoxy resin, and significantly improves the aging resistance, adhesion and waterproof ability of the epoxy resin coating while improving the antifouling performance of the epoxy resin coating.

[0007] In order to achieve the above object, the first aspect of the present invention provides a curing active branched isobutylene quaternary phosphonium salt polymer, wherein the polymer 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 quaternary phosphonium salt group, and in the polymer, 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 curing active branched isobutylene quaternary phosphonium salt ion polymer, wherein the preparation method comprises the following steps:

[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 to a solution of the halogenated branched isobutylene copolymer to carry out an ionization reaction to obtain the curing active branched isobutylene quaternary phosphonium 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 molar amount of the phosphine 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 quaternary phosphonium 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 an epoxy resin and the above-mentioned curing active branched isobutylene quaternary phosphonium salt copolymer;

[0020] The component B comprises a curing agent.

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

[0022] Through the above technical scheme, the curable active branched isobutylene quaternary phosphonium salt copolymer and preparation method, curable epoxy resin composition and waterproof and antifouling coating provided by the present invention achieve the following beneficial effects:

[0023] In the present invention, the curing active branched isobutylene quaternary phosphonium salt polymer has a star-shaped branched structure including multiple branches, and the branched structure simultaneously carries a quaternary phosphonium salt group and a curing active functional group, has good compatibility with epoxy resin, can be used and co-cured with epoxy resin, and significantly improves the aging resistance, adhesion and waterproof ability of the epoxy resin coating while improving the antifouling performance of the epoxy resin coating.

[0024] Furthermore, the curing active branched isobutylene quaternary phosphonium salt polymer described in the present invention not only has the hydrophobic structure of the polyolefin main chain and the hydrophilic structure of the quaternary phosphonium salt functional group, but can better balance the hydrophobic and hydrophilic performance requirements of underwater coatings. Due to the branched pre-crosslinked main chain structure and curing active groups, as well as co-crosslinking and curing with the epoxy resin for underwater coatings, the crosslinking density of the antibacterial polymer is enhanced, and the antibacterial agent is prevented from migrating in the coating matrix or swelling in water to affect the performance of the underwater coating material. The quaternary phosphonium salt groups that are largely immobilized by the macromolecular chain not only provide efficient sterilization, algaecide, and antifouling capabilities, but also have good bonding strength with polar surfaces such as metals and cement construction facilities, improve adhesion, and can replace the use of metal poisons, giving the underwater coating material a more durable antifouling ability. 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 quaternary phosphonium salt polymer, wherein the polymer 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 quaternary phosphonium salt group, and in the polymer, Q1 and Q2 are not all H at the same time.

[0033] In the present invention, the curing active branched isobutylene quaternary phosphonium salt polymer has a star-shaped branched structure including multiple branches, and the branched structure simultaneously carries a quaternary phosphonium salt group and a curing active functional group, has good compatibility with epoxy resin, can be used and co-cured with epoxy resin, and significantly improves the aging resistance, adhesion and waterproof ability of the epoxy resin coating while improving the antifouling performance 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 polymer, the content of the isobutylene structural unit is 60-80 mol%.

[0038] In the present invention, the curing active branched isobutylene quaternary phosphonium 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] Furthermore, based on the total molar amount of the polymer, the content of the isobutylene structural unit is 65-75 mol%.

[0040] According to the present invention, based on the total molar amount of the polymer, the content of the quaternary phosphonium salt group is 5-25 mol%.

[0041] In the present invention, when the content of each structural unit in the polymer meets the above range, the polymer has excellent compatibility with the coating resin, and can improve the crosslinking density of the resin containing the polymer and the adhesion between the resin and the surface of the substrate, reduce the dimensional shrinkage of the resin after curing, and the cured resin coating is not easy to crack, and has excellent water resistance and stable and long-lasting waterproof and antifouling properties.

[0042] Furthermore, based on the total molar amount of the polymer, the content of the quaternary phosphonium salt group is 8-20 mol%.

[0043] According to the present invention, the quaternary phosphonium salt group has a structure shown in formula (1);

[0044]

[0045] 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 X is Cl or Br.

[0046] Furthermore, R1, R2, and R3 are C6-C 10 X is Br.

[0047] Furthermore, R1, R2, and R3 are phenyl groups; and X is Br.

[0048] According to the present invention, based on the total molar amount of the polymer, the content of the curing active functional groups is 5-25 mol%.

[0049] In the present invention, when the content of the curing active functional group meets the above range, it is used in combination with the epoxy resin to have a high crosslinking density, is not prone to swelling and blistering after long-term immersion in water, and has better waterproof and water-resistant effects.

[0050] Furthermore, based on the total molar amount of the polymer, the content of the curing active functional group is 6-22 mol%.

[0051] According to the present invention, the curing active functional group is an active group capable of reacting with an amine curing agent. Preferably, the curing active functional group is a group having an active halogen.

[0052] According to the present invention, the polymer comprises at least three branched chains.

[0053] In the present invention, the polymer comprising at least three branches refers to a star-shaped polymer with at least three branches radiating from a central point.

[0054] The second aspect of the present invention provides a method for preparing a cured active branched isobutylene quaternary phosphonium salt polymer, wherein the preparation method comprises the following steps:

[0055] (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;

[0056] (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;

[0057] (3) adding a phosphine compound to a solution of the halogenated branched isobutylene copolymer to carry out an ionization reaction to obtain the curing active branched isobutylene quaternary phosphonium salt copolymer;

[0058] The initiator solution comprises at least one multifunctional initiator, at least one activator, at least one co-initiator and at least one halogenated alkane;

[0059] The molar amount of the phosphine compound is 0.2-0.8 times that of the halogen.

[0060] In the preparation method of the curing active branched isobutylene quaternary phosphonium salt polymer, in the presence of a multifunctional initiator, a cationic polymerization reaction of isobutylene and alkylstyrene is carried out in a microchannel reactor to prepare an isobutylene-alkylstyrene polymer with a branched structure, and a curing active branched isobutylene quaternary phosphonium salt polymer is prepared by halogenation reaction and ionization reaction, especially by controlling the dosage ratio of the phosphine compound to the halogen in the ionization reaction process. The curing active branched isobutylene quaternary phosphonium salt polymer has a star-shaped branched structure including a plurality of branches, and the branched structure simultaneously carries a high content of quaternary phosphonium groups and curing active functional groups, has good compatibility with epoxy resin, can be used and co-cured with the epoxy resin, and significantly improves the aging resistance, adhesion and waterproof ability of the epoxy resin coating while improving the antifouling performance of the epoxy resin coating.

[0061] Cationic polymerization

[0062] 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.

[0063] Furthermore, the molar ratio of the multifunctional initiator, the activator and the co-initiator is 1:0.5-1.2:5-10.

[0064] According to the present invention, the multifunctional initiator is an organic compound containing at least three functional groups having cationic initiation reaction activity.

[0065] 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.

[0066] 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.

[0067] 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).

[0068] 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.

[0069] 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%.

[0070] 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.

[0071] 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%.

[0072] 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, monochlorobutane, preferably dichloromethane and carbon tetrachloride.

[0073] 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%.

[0074] 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.

[0075] Furthermore, based on the total volume of the alkane and the halogenated alkane, the volume percentage of the alkane is 40-60 vol%.

[0076] According to the present invention, the mass concentration of the monomer solution is 5-50%, preferably 10-40%.

[0077] 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.

[0078] 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%.

[0079] 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.

[0080] 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%.

[0081] 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.

[0082] Furthermore, the conditions of the cationic polymerization reaction include: reaction time of 8-20 min; reaction temperature of -30°C to -10°C.

[0083] 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.

[0084] 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.

[0085] 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.

[0086] 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.

[0087] Furthermore, the weight average molecular weight Mw of the branched isobutylene-based copolymer is 5×10 3g / mol-1.5×10 4 g / mol, and the molecular weight distribution coefficient Mw / Mn is 1.6-2.2.

[0088] 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.

[0089] 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.

[0090] 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.

[0091] In the present invention, preferably, the tubular reactor is a coil reactor to ensure sufficient residence time for the reaction to proceed completely.

[0092] 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.

[0093] In a specific embodiment of the present invention, Figure 1 As shown, the cationic polymerization reaction is carried out according to the following steps:

[0094] (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;

[0095] (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;

[0096] (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;

[0097] (4) the material flowing out of the microchannel reactor enters the tubular reactor to continue the cationic polymerization reaction;

[0098] (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.

[0099] Halogenation reaction

[0100] In the present invention, the halogenation reaction of the branched isobutylene-based copolymer is carried out in a dark box protected from light.

[0101] 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 1:0.6-1.2, preferably 1:0.7-1.

[0102] According to the present invention, the halogenation reaction is carried out under the irradiation of visible light.

[0103] 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.

[0104] In a specific embodiment of the present invention, the halogenation reaction is carried out according to the following steps:

[0105] 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;

[0106] 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;

[0107] 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.

[0108] 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.

[0109] In a specific embodiment of the present invention, the halogen is liquid bromine.

[0110] Cationic salification

[0111] According to the present invention, the molar amount of the phosphine compound is 0.2-0.8 times, preferably 0.3-0.7 times, the molar amount of the halogen.

[0112] In the present invention, when the molar amount of the phosphine compound is controlled to meet the above range, the required amount of cationic salt can be obtained while retaining a high content of active halogen groups, so that it can be used in conjunction with the coating resin and achieve co-crosslinking and curing with the coating resin under the action of the curing agent.

[0113] According to the present invention, the phosphine compound has a structure shown in Formula I;

[0114]

[0115] 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.

[0116] Furthermore, R1, R2, and R3 are C6-C 10 further, R1, R2, and R3 are phenyl.

[0117] 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.

[0118] According to the present invention, the conditions of the ionization reaction include: a reaction temperature of 70-90° C. and a reaction time of 6-10 h.

[0119] In one embodiment of the present invention, the functionalization reaction is carried out according to the following steps:

[0120] (i) injecting a halogenated branched isobutylene polymer solution of a certain concentration 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 6-10 hours, and the reaction system gradually changes from a solution state to a slurry state;

[0121] (ii) 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 quaternary phosphonium salt polymer.

[0122] The third aspect of the present invention provides a curing active branched isobutylene quaternary phosphonium salt polymer prepared by the above preparation method.

[0123] 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;

[0124] The component A comprises an epoxy resin and the above-mentioned curing active branched isobutylene quaternary phosphonium salt polymer;

[0125] The component B comprises a curing agent.

[0126] In the present invention, the curable epoxy resin composition contains the above-mentioned curing active branched isobutylene quaternary phosphonium salt polymer. The curing active functional groups contained in the polymer are cross-linked and cured with the epoxy resin under the action of the curing agent, thereby reducing the brittleness of the epoxy resin and improving the adhesion, anti-fouling, aging resistance and waterproof performance of the epoxy resin coating.

[0127] In the present invention, the epoxy resin includes but is not limited to glycidyl epoxy resin and non-glycidyl epoxy resin.

[0128] 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 resins, linear phenolic epoxy resins, aliphatic glycidyl ether resins, etc.; the glycidyl ester epoxy resins include diglycidyl phthalate. The non-glycidyl epoxy resins include but are not limited to alicyclic epoxy resins and epoxidized olefin epoxy resins. The present invention preferably uses bisphenol A epoxy resins, and more preferably uses bisphenol A epoxy resins with an epoxy value of 0.1-0.6.

[0129] According to the present invention, the mass ratio of the epoxy resin to the curing active branched isobutylene quaternary phosphonium salt copolymer in the component A is 1:0.1-1.5.

[0130] 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.

[0131] 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.

[0132] 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.

[0133] 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.

[0134] A fifth aspect of the present invention provides a waterproof and antifouling coating, wherein the waterproof and antifouling coating is obtained by curing the above-mentioned curable resin composition.

[0135] In the present invention, the waterproof and antifouling coating has satisfactory waterproof and antifouling functions, and is suitable for protective coatings of engineering facilities that are immersed in water for a long time, such as underwater engineering, buildings and other facilities. While waterproofing, it effectively prevents the adhesion and pollution of water-contaminated microorganisms on the surface of the facilities, making the use of the coating material more durable. At the same time, the quaternary phosphite groups in the waterproof and antifouling coating are not easy to migrate or swell in water, and can provide efficient and lasting sterilization, algaecide, and antifouling capabilities, and have good bonding strength with polar surfaces such as metals and cement building facilities, improve adhesion, and can replace the use of metal poisons, giving underwater coating materials more lasting antifouling capabilities.

[0136] In the present invention, unless otherwise specified, the room temperature is 25°C.

[0137] The present invention will be described in detail below through examples.

[0138] 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.

[0139] The monomer polymerization conversion of the branched isobutylene-based copolymer was measured by headspace method using Agilent 7890 gas chromatograph.

[0140] The content of each structural unit in the branched isobutylene-based copolymer and the curing active branched isobutylene-based composite cationic salt copolymer was measured using an AVANCE NEO 600M nuclear magnetic resonance spectrometer produced by Bruker Company of Switzerland.

[0141] 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.

[0142] The mechanical property test of the resin was carried out in accordance with GB / T 2567-2008 "Test Method for Properties of Resin Castings". The resin was cured at room temperature for 7 days after molding, and then the tensile strength, elongation at break, compressive strength and shear strength of the material were tested on an RGM-100 microcomputer-controlled electronic universal testing machine.

[0143] For the resin bonding strength test, an A4-sized Q345 steel plate specimen was immersed in water for 24 hours. After a simple surface treatment, a layer of epoxy coating material with a thickness of about 3 mm was applied. The specimen was then cured underwater at room temperature for 7 days. The underwater positive tensile bonding strength was tested using a carbon fiber bonding strength tester.

[0144] The bond strength was tested using a PosiTest AT-A adhesion tester.

[0145] Resin abrasion resistance test, according to the ring method in DL / T5193, 40m / s flow rate test.

[0146] The raw materials used in the examples and comparative examples are all commercially available.

[0147] The details are described in the following examples.

[0148] Example 1

[0149] All reaction experiments were carried out under nitrogen protection.

[0150] (1) Preparation of branched isobutylene-based copolymers

[0151] Initiator solution logistics 1: add 150 mL of refined dichloromethane solvent, 0.0008 mol of tricumyl chloride and 0.0006 mol of tetrachlorobenzoquinone into a 250 mL double-necked glass bottle, precool to -10°C after dissolving, add 0.005 mol of ethylaluminum dichloride, and prepare an initiator solution for use; wherein the molar ratio of the initiator, the activator and the co-initiator is 1:0.75:6.25.

[0152] Monomer solution logistics 2: Add 600 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 1.52 mol of isobutylene monomer, 0.52 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 75 mol%, and the amount of molecular weight regulator is 1.43 mol%.

[0153] 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 96.3%.

[0154] 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%.

[0155] 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.

[0156] The weight average molecular weight Mw of the branched isobutylene-based copolymer P1 was determined to be 7960 g / mol, and the molecular weight distribution coefficient Mw / Mn was 1.92.

[0157] (2) Bromination reaction of branched isobutylene copolymer

[0158] Preparation of liquid bromine solution: Take 0.52 mol of liquid bromine and add it into 250 mL of carbon tetrachloride and mix well for later use;

[0159] Under stirring conditions, in a dark box, 0.57 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 150W light source with a wavelength of 630 nm for bromination reaction, and the pulse time was 12 s. The molar ratio of p-methylstyrene to bromine in the branched isobutylene copolymer P1 was 1:1.

[0160] 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 branched brominated isobutylene-based copolymer solution.

[0161] 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.

[0162] The total bromine content of the brominated branched isobutylene-based copolymer XP1 was determined to be 21.4 wt%.

[0163] (3) Quaternary Phosphonium Saltization of Brominated Branched Isobutylene Copolymers

[0164] Triphenylphosphine solution: add 0.35 mol triphenylphosphine to 150 mL carbon tetrachloride solvent and dissolve for later use; wherein the molar ratio of triphenylphosphine to bromine is 0.67:1;

[0165] Add triphenylphosphine solution to the solution containing brominated branched isobutylene copolymer XP1, raise the temperature to 80°C and keep reflux reaction for 10 hours, and the reaction system gradually changes from solution state to slurry state;

[0166] 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 quaternary phosphonium salt copolymer, which is recorded as BBIMS-CA-1.

[0167] The content of each structural unit in the curing active branched isobutylene quaternary phosphonium salt copolymer was measured, and the results are shown in Table 1.

[0168] Example 2

[0169] (1) Preparation of branched isobutylene-based copolymers

[0170] Initiator solution stream 1: the same initiator solution as in Example 1 is used for standby use;

[0171] 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 1.04 mol of isobutylene monomer, 0.51 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 68 mol%, and the amount of molecular weight regulator is 1.26 mol%.

[0172] The microchannel reactor of Example 1 is still used, except that the reaction temperature is set at -20°C, the flow rate of the initiator solution is 0.9 mL / min, the flow rate of the monomer solution is 6 mL / min, the total time for the mixture solution to pass through the 3rd to 10th modules is 8.5 min, and the monomer polymerization conversion rate reaches 96.2%.

[0173] The material flowing out of the microchannel reactor enters the tubular reactor, 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%.

[0174] The rest is the same as step (1) in Example 1.

[0175] The weight average molecular weight Mw of the branched isobutylene-based copolymer P2 was determined to be 12860 g / mol, and the molecular weight distribution coefficient Mw / Mn was 1.78.

[0176] (2) Bromination reaction of branched isobutylene copolymer

[0177] Preparation of liquid bromine solution: Take 0.46 mol of liquid bromine and add it into 250 mL of carbon tetrachloride and mix well for later use;

[0178] The same bromination reaction method as step (2) in Example 1 was used, except that 0.55 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 bromine in the branched isobutylene copolymer P2 was 1:0.9.

[0179] The rest is the same as step (2) in Example 1.

[0180] The total bromine content of the brominated branched isobutylene-based copolymer XP2 was determined to be 22.9 wt%.

[0181] (3) Quaternary Phosphonium Saltization of Brominated Branched Isobutylene Copolymers

[0182] Triphenylphosphine solution: add 0.22 mol triphenylphosphine to 100 mL carbon tetrachloride solvent and dissolve for later use; wherein the molar ratio of triphenylphosphine to bromine is 0.48:1;

[0183] Add triphenylphosphine solution to the solution containing brominated branched isobutylene copolymer XP2, raise the temperature to 80°C and keep reflux reaction for 8 hours, and the reaction system gradually changes from solution state to slurry state;

[0184] 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 quaternary phosphonium salt copolymer, which is recorded as BBIMS-CA-2.

[0185] The content of each structural unit in the curing active branched isobutylene quaternary phosphonium salt copolymer was measured, and the results are shown in Table 1.

[0186] Example 3

[0187] (1) Preparation of branched isobutylene-based copolymers

[0188] Initiator solution logistics 1: add 150 mL of refined dichloromethane solvent, 0.0006 mol of tricumyl chloride and 0.0005 mol of tetrachlorobenzoquinone to a 250 mL double-necked glass bottle, precool to -10°C after dissolving, add 0.005 mol of ethylaluminum dichloride, and prepare an initiator solution for use; wherein the molar ratio of the initiator, the activator and the co-initiator is 1:0.83:8.33.

[0189] Monomer solution logistics 2: Add 600 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 1.2 mol of isobutylene monomer, 0.7 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 65 mol%, and the amount of molecular weight regulator is 2.5 mol%.

[0190] The rest is the same as step (1) in Example 1.

[0191] The weight average molecular weight Mw of the branched isobutylene-based copolymer P3 was determined to be 5850 g / mol, and the molecular weight distribution coefficient Mw / Mn was 2.01.

[0192] (2) Bromination reaction of branched isobutylene copolymer

[0193] 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;

[0194] Under stirring conditions, in a dark box, 0.67 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 150W light source with a wavelength of 595 nm for bromination reaction, and the pulse time was 10 s. Among them, the molar ratio of p-methylstyrene to bromine in the branched isobutylene copolymer P3 was 1:0.8.

[0195] The rest is the same as step (2) in Example 1.

[0196] The total bromine content of the brominated branched isobutylene-based copolymer XP3 was determined to be 22.9 wt%.

[0197] (3) Quaternary Phosphonium Saltization of Brominated Branched Isobutylene Copolymers

[0198] Triphenylphosphine solution: add 0.22 mol of triphenylphosphine to 100 mL of carbon tetrachloride solvent and dissolve for later use; wherein the molar ratio of triphenylphosphine to bromine is 0.4:1;

[0199] The rest of the process was the same as step (3) in Example 1 to obtain a cured active branched isobutylene quaternary phosphonium salt copolymer, which was designated as BBIMS-CA-3.

[0200] The content of each structural unit in the curing active branched isobutylene quaternary phosphonium salt copolymer was measured, and the results are shown in Table 1.

[0201] Example 4

[0202] (1) Preparation of branched isobutylene-based copolymers

[0203] Same as step (1) in Example 3.

[0204] The weight average molecular weight Mw of the branched isobutylene-based copolymer P4 was determined to be 5360 g / mol, and the molecular weight distribution coefficient Mw / Mn was 1.95.

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

[0206] 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;

[0207] Under stirring conditions, in a dark box, 0.76 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 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 bromine in the branched isobutylene copolymer P4 was 1:0.9.

[0208] The rest is the same as step (2) in Example 3.

[0209] The total bromine content of the brominated branched isobutylene-based copolymer XP4 was determined to be 24.2 wt%.

[0210] (3) Quaternary Phosphonium Saltization of Brominated Branched Isobutylene Copolymers

[0211] Triphenylphosphine solution: add 0.21 mol of triphenylphosphine to 100 mL of carbon tetrachloride solvent and dissolve for later use; wherein the molar ratio of triphenylphosphine to bromine is 0.33:1;

[0212] The rest of the process was the same as step (3) in Example 1 to obtain a cured active branched isobutylene quaternary phosphonium salt copolymer, which was designated as BBIMS-CA-4.

[0213] The content of each structural unit in the curing active branched isobutylene quaternary phosphonium salt copolymer was measured, and the results are shown in Table 1.

[0214] Example 5

[0215] (1) Preparation of branched isobutylene-based copolymers

[0216] Initiator solution logistics 1: Same as Example 3.

[0217] 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 1.2 mol of isobutylene monomer, 0.58 mol of p-methylstyrene monomer, and 0.08 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 4.12 mol%.

[0218] The rest is the same as step (1) in Example 1.

[0219] The weight average molecular weight Mw of the branched isobutylene-based copolymer P5 was determined to be 4340 g / mol, and the molecular weight distribution coefficient Mw / Mn was 2.13.

[0220] (2) Bromination reaction of branched isobutylene copolymer

[0221] Preparation of liquid bromine solution: Take 0.58 mol of liquid bromine and add it into 250 mL of carbon tetrachloride and mix well for later use;

[0222] Under stirring conditions, in a dark box, 0.56 mol of sodium bicarbonate was added to a reactor containing a solution of the branched isobutylene copolymer P4. 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. Among them, the molar ratio of p-methylstyrene to bromine in the branched isobutylene copolymer P5 was 1:1.

[0223] The rest is the same as step (2) in Example 1.

[0224] The total bromine content of the brominated branched isobutylene-based copolymer XP5 was determined to be 23.9 wt%.

[0225] (3) Quaternary Phosphonium Saltization of Brominated Branched Isobutylene Copolymers

[0226] Triphenylphosphine solution: add 0.36 mol triphenylphosphine to 150 mL carbon tetrachloride solvent and dissolve for later use; wherein the molar ratio of triphenylphosphine to bromine is 0.62:1;

[0227] The rest of the process was the same as step (3) in Example 1 to obtain a cured active branched isobutylene quaternary phosphonium salt copolymer, which was designated as BBIMS-CA-5.

[0228] The content of each structural unit in the curing active branched isobutylene quaternary phosphonium salt copolymer was measured, and the results are shown in Table 1.

[0229] Comparative Example 1

[0230] (1) Preparation of branched isobutylene-based copolymers

[0231] Initiator solution stream 1: an initiator solution prepared in the same manner as in Example 1 for standby use;

[0232] Monomer solution stream 2: a monomer solution prepared in the same manner as in Example 1 for standby use;

[0233] The same polymerization method as step (1) in Example 1 was adopted.

[0234] The weight average molecular weight Mw of the branched isobutylene-based copolymer DP1 was determined to be 7340 g / mol, and the molecular weight distribution coefficient Mw / Mn was 2.03.

[0235] (2) Bromination reaction of branched isobutylene copolymer

[0236] Preparation of liquid bromine solution: Take 0.36 mol of liquid bromine and add it into 200 mL of carbon tetrachloride and mix well for later use;

[0237] The same bromination reaction method as step (2) in Example 1 was adopted, except that 0.44 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 1:0.7.

[0238] The rest is the same as step (2) in Example 1.

[0239] The total bromine content of the brominated branched isobutylene-based copolymer DXP1 was determined to be 15.9 wt%.

[0240] (3) Quaternary Phosphonium Saltization of Brominated Branched Isobutylene Copolymers

[0241] Triphenylphosphine solution: add 0.4 mol triphenylphosphine to 200 mL carbon tetrachloride solvent and dissolve for later use; wherein the molar ratio of triphenylphosphine to bromine is 1.1:1;

[0242] The rest of the process was the same as in Example 1, and a branched isobutylene quaternary phosphonium salt copolymer without curing active groups was obtained, which was recorded as BBIMS-CD.

[0243] The content of each structural unit in the branched isobutylene quaternary phosphonium salt copolymer without curing active groups was measured, and the results are shown in Table 1.

[0244] Table 1

[0245]

[0246]

[0247] 1 Based on the total molar weight of the copolymer

[0248] Application example - waterproof and antifouling coating

[0249] The waterproof and antifouling coating was prepared according to the following method. The specific formula is shown in Table 2:

[0250] Preparation of component S1: First, the solvent (butanol and xylene), liquid epoxy resin (E51 and E54), BBIMS of the embodiment and the comparative example, toughening agent (dioctyl phthalate), and film-forming agent (N160) are mixed and stirred evenly, and silicon dioxide is added to the mixed liquid in batches under the 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 vacuum stirred and defoamed for 30 minutes.

[0251] Preparation of component S2: First, the solvent (butanol and xylene), curing agent (triethylenetetramine), curing accelerator (tetramer), and film-forming agent (N160) are mixed and stirred evenly. Under the stirring of a high-speed shear dispersant, silicon dioxide is added to the mixed liquid in batches and stirred at high speed for 15 minutes. Then, barium sulfate and quartz powder are added in batches and stirred at high speed until the system becomes a uniform paste. Finally, vacuum and stir to remove bubbles for 30 minutes.

[0252] For the solvent, filler and auxiliary components added to both S1 and S2, including butanol, xylene, film former, silicon dioxide, barium sulfate, and quartz powder, 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 obtain underwater waterproof and antifouling epoxy resin coating.

[0253] Table 2

[0254]

[0255]

[0256] The mechanical properties and bonding strength of the epoxy resin coating after curing were tested, specifically:

[0257] 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.

[0258] 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.

[0259] The abrasion resistance test is carried out according to the ring method in DL / T5193 and the flow rate is 40m / s.

[0260] The test results are shown in Table 3.

[0261] Table 3

[0262]

[0263]

[0264] As can be seen from Table 3, when the BBIMS provided by the present invention is used in equal amounts 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 and abrasion resistance gradually decrease, indicating that BBIMS has the effect of toughening epoxy resin, but the wear resistance is not as good as that of epoxy resin. The BBIMS without curing activity provided in the comparative example is used in combination with epoxy resin, which only acts as a toughening agent, resulting in a significant decrease in tensile strength, compressive strength and abrasion resistance.

[0265] The coatings prepared in Application Example 1, Application Example 2, Application Example 5, Application Example 7 and Comparative Application Example 1 were scraped and applied on the surface of a 20×20×1cm ceramic tile. After applying twice with an interval of 24 hours, the tiles were cured at room temperature for 7 days. In the summer from June to August, when aquatic microorganisms are proliferating vigorously, the ceramic tiles were immersed in an ornamental fish pond to receive sunlight. The tiles were taken out every half month to observe the pollution and damage of the coating on the surface of the tiles, and records were made. After 3 months, the tiles were taken out, the surface pollutants were brushed off, and the tiles were placed in an oven and baked at 65°C for 24 hours to observe the changes on the coating surface. The specific observation phenomena are shown in Table 4 below.

[0266] Table 4

[0267]

[0268]

[0269] It can be seen that the cured active branched isobutylene quaternary phosphonium salt polymer provided by the present invention is used in combination with epoxy resin to prepare underwater antifouling coatings, which can significantly improve the aging resistance and anti-pollution ability of epoxy resin coating materials. It is suitable for various viewing pools, fish ponds, swimming pools, bathing pools and other places and various underwater engineering facilities, has a more satisfactory service life and anti-pollution ability, and can effectively inhibit the adhesion and reproduction of harmful microorganisms in the water environment on the coating surface.

[0270] 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 cured active branched isobutylene quaternary phosphonium salt ionomer, characterized in that: The polymer has a star-branched structure including a plurality of branched 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 quaternary phosphonium salt group, and in the polymer, Q1 and Q2 are not all H at the same time.

2. The polymer according to claim 1, wherein Based on the total molar amount of the polymer, the content of the isobutylene structural unit is 60-80 mol %, preferably 65-75 mol %.

3. The polymer according to claim 1 or 2, wherein Based on the total molar amount of the polymer, the content of the quaternary phosphonium salt group is 5-25 mol%, preferably 8-20 mol%; Preferably, the quaternary phosphonium salt group has a structure shown in formula (1); 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 X is Cl or Br.

4. The polymer according to any one of claims 1 to 3, wherein Based on the total molar amount of the polymer, the content of the curing active functional group is 5-25 mol%, preferably 6-22 mol%; Preferably, the curing active functional group is a group having an active halogen.

5. The polymer according to any one of claims 1 to 4, wherein The polymer comprises at least three branched chains.

6. A method for preparing a cured active branched isobutylene quaternary phosphonium salt ion polymer, characterized in that: The preparation method comprises the following steps: (1) contacting and mixing an initiator solution and a monomer solution in a microchannel reactor under cationic polymerization conditions to carry out a cationic polymerization reaction to obtain a solution containing a branched isobutylene-alkylstyrene polymer; (2) contacting the branched isobutylene-alkylstyrene polymer solution with a halogen to perform a halogenation reaction to obtain a solution containing a halogenated branched isobutylene-based polymer; (3) adding a phosphine compound to a solution of the halogenated branched isobutylene olefin polymer to carry out an ionization reaction to obtain the cured active branched isobutylene quaternary phosphonium salt polymer; 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 molar amount of the phosphine compound is 0.2-0.8 times that of the halogen.

7. The preparation method according to claim 6, 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.

8. The preparation method according to claim 6 or 7, wherein: The molar amount of the phosphine compound is 0.3-0.7 times that of the halogen.

9. The preparation method according to any one of claims 6 to 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 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%.

10. The preparation method according to any one of claims 6 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 6 to 10, 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.

12. The preparation method according to any one of claims 6 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, 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.

13. The preparation method according to any one of claims 6 to 12, wherein: The molar ratio of the branched isobutylene-alkylstyrene copolymer to the halogen is 1:0.6-1.2, preferably 1:0.7-1, based on the molar content of the structural unit of the alkylstyrene; Preferably, the halogenation reaction is initiated 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 10-15s.

14. The preparation method according to any one of claims 6 to 13, 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.

15. The preparation method according to any one of claims 6 to 14, wherein: The conditions of the ionization reaction include: reaction temperature of 70-90° C., and reaction time of 6-10 h.

16. A curing active branched isobutylene quaternary phosphonium salt copolymer prepared by the preparation method according to any one of claims 6 to 15.

17. 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 quaternary phosphonium salt copolymer as described in any one of claims 1 to 5 and 16; The component B comprises a curing agent.

18. The curable resin composition according to claim 17, wherein In terms of mass, the mass ratio of the epoxy resin to the curing active branched isobutylene quaternary phosphonium salt copolymer in the component A is 1:0.1-1.5; Preferably, the mass ratio of the epoxy resin to the curing active branched isobutylene quaternary phosphonium salt copolymer in the component A is 1:0.2-1 by mass.

19. The curable resin composition according to claim 17 or 18, wherein The curing agent is a polyamine compound.

20. A waterproof and antifouling coating, characterized in that: The waterproof and antifouling coating is obtained by curing the curable resin composition according to any one of claims 17 to 19.

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