Self-polishing polyurethane antifouling resin and preparation method thereof, intrinsic self-polishing polyurethane antifouling paint and application

Abstract

The application provides a self-polishing polyurethane antifouling resin and a preparation method thereof, an intrinsic self-polishing polyurethane antifouling paint and application, and relates to the technical field of paints. The preparation method of the intrinsic self-polishing polyurethane antifouling paint comprises: preparing by addition reaction of a zinc carboxylate intermediate and a diol amine; wherein the zinc carboxylate intermediate is a zinc carboxylate salt containing a terminal carboxyl group; the zinc carboxylate intermediate is obtained by neutralization reaction after mixing of a first carboxylic acid monomer, a second carboxylic acid monomer and zinc oxide; and the self-polishing polyurethane antifouling resin can be obtained by addition reaction of the zinc carboxylate salt containing a terminal carboxyl group and diethanolamine. The polyurethane coating prepared from the self-polishing polyurethane antifouling resin can slowly and uniformly hydrolyze in seawater to generate an amphoteric ion with an antifouling function. Especially when the self-polishing polyurethane antifouling resin is used in combination with an antifouling agent, the antifouling agent is slowly released when the polyurethane coating hydrolyzes, so that a synergistic antifouling effect is achieved.

Description

TECHNICAL FIELD

[0001] The present application belongs to the technical field of coatings, and in particular relates to a self-polishing polyurethane antifouling resin, a preparation method thereof, an intrinsic self-polishing polyurethane antifouling paint and application. BACKGROUND

[0002] In the marine environment, marine equipment such as steel pipe piles, offshore oil platforms, ships, buoys, etc. in the seawater immersion zone often suffer from various marine biofouling. If effective antifouling measures are not taken, the rampant growth of marine organisms not only leads to an increase in the weight of marine equipment, but also affects the service performance of the equipment. Antifouling paint is a special coating applied to the underwater parts of ships, marine equipment, etc. for inhibiting the attachment and growth of marine organisms (such as barnacles, algae, shellfish, etc.). Applying antifouling paint is the most effective and convenient protective measure to reduce the rapid growth of marine organisms on marine equipment.

[0003] Currently, the mainstream antifouling paint mainly includes tin-free self-polishing antifouling paint (mainly using copper acrylate resin as the main film-forming material) and low-surface-energy antifouling paint (mainly using silicone resin as the main film-forming material), and the antifouling paint needs to take into account the antifouling effect and environmental protection requirements. Whether it is copper acrylate resin or silicone resin, an antifouling agent needs to be added to the resin to achieve the antifouling function, and the resin itself has no antifouling effect. Chinese Invention Patent CN105542607A discloses a betaine-type zwitterionic modified acrylate self-polishing antifouling paint and a preparation method thereof, and the betaine-type functional zwitterionic resin can rely on its unique quaternary ammonium salt and sulfonate functional groups to cause the cell walls of marine microorganisms attached to the surface of the coating to rupture and die, and then easily fall off under the action of water flow shear or other external forces, which can effectively prevent or slow down the adhesion of green algae and diatom spores to the substrate to form a microbial mucosa, thereby achieving the effects of antifouling and fouling release. Therefore, the combination of the betaine-type functional zwitterionic antifouling effect and the self-polishing antifouling effect can effectively compensate for the respective defects and enhance the antifouling performance of the antifouling paint. However, it is found in the use process that excellent antifouling effect is exhibited in the Shenzhen Daya Bay sea area (salinity of 25‰-30.69‰), but when the self-polishing antifouling paint is used continuously for 6 months in a marine environment with higher salinity (for example, the Sanya sea area), the coating surface appears to have blistering, peeling and other phenomena due to factors such as hydrolysis of the acrylate, which affects the protection of the substrate, and therefore a more long-acting antifouling paint is needed.

[0004] Based on this, the present application provides a self-polishing polyurethane antifouling resin based on the prior art, which has intrinsic antifouling efficacy and can also produce a synergistic effect between the resin and the antifouling agent, achieving synergistic antifouling efficacy and providing a long-acting antifouling solution for the underwater region of marine ships or marine equipment. SUMMARY

[0005] The present application aims to provide a self-polishing polyurethane antifouling resin and a preparation method thereof, an intrinsic self-polishing polyurethane antifouling paint and application, so as to overcome the shortcomings of the prior art.

[0006] As one of the purposes of the application, the present application provides a preparation method of a self-polishing polyurethane antifouling resin, comprising: preparing by addition reaction of a zinc carboxylate intermediate and a glycol amine; wherein the zinc carboxylate intermediate is a zinc carboxylate salt containing a terminal carboxyl group; the zinc carboxylate intermediate is obtained by neutralization reaction of a first carboxylic acid monomer, a second carboxylic acid monomer and zinc oxide.

[0007] As a preferred embodiment, the first carboxylic acid monomer is a terminal double bond carboxylic acid.

[0008] As a preferred embodiment, the second carboxylic acid monomer is a straight-chain saturated carboxylic acid.

[0009] As a preferred embodiment, the molar ratio of the first carboxylic acid monomer, the second carboxylic acid monomer and zinc oxide is 1:1~1.2:0.8~1.

[0010] As a preferred embodiment, the molar ratio of the first carboxylic acid monomer and the glycol amine is 1:0.9~1.

[0011] As a preferred embodiment, the first carboxylic acid monomer is any one of acrylic acid and methacrylic acid.

[0012] As a preferred embodiment, the second carboxylic acid monomer is any one of acetic acid, propionic acid and n-butanoic acid.

[0013] As a preferred embodiment, the glycol amine is diethanolamine.

[0014] Preferably, the neutralization reaction comprises: adding the first carboxylic acid monomer, the second carboxylic acid monomer and zinc oxide into a reaction solvent, under the protection of an inert gas, stirring at 65~80℃ and 200~300r / min for 2~5h.

[0015] Preferably, the inert gas is argon.

[0016] As a preferred embodiment, the reaction solvent is a mixed solvent of xylene and propylene glycol methyl ether acetate.

[0017] As a preferred embodiment, the mass ratio of xylene to propylene glycol methyl ether acetate is 1:0.9~1.

[0018] As a preferred embodiment, the conditions of the addition reaction include: reducing the temperature to 20-35℃, adding the diol amine into the zinc carboxylate intermediate under the protection of inert gas, and stirring the reaction for 20-24h, thereby obtaining the self-polishing polyurethane antifouling resin.

[0019] As a second aspect of the application, the application further provides a self-polishing polyurethane antifouling resin prepared by the preparation method.

[0020] As a third aspect of the application, the application further provides an intrinsic self-polishing polyurethane antifouling coating, which at least comprises the self-polishing polyurethane antifouling resin provided in the above technical solution.

[0021] As a preferred embodiment, the components of the intrinsic self-polishing polyurethane antifouling coating comprise, in terms of mass parts, the self-polishing polyurethane antifouling resin 15-25 parts, an antifouling agent 15-30 parts, a filler 10-20 parts, and an organic solvent 20-30 parts.

[0022] As a preferred embodiment, the organic solvent is xylene or ethyl acetate.

[0023] As a preferred embodiment, the filler is selected from a combination of one or more of iron oxide, barium sulfate, and talc powder.

[0024] As a preferred embodiment, the antifouling agent comprises a combination of cuprous oxide and zineb.

[0025] As a preferred embodiment, the mass ratio of the antifouling agent to the self-polishing polyurethane antifouling resin is 1-2:1.

[0026] As a preferred embodiment, the mass ratio of cuprous oxide to zineb is 1:1-3:1.

[0027] As a preferred embodiment, the intrinsic self-polishing polyurethane antifouling coating further comprises an auxiliary agent.

[0028] As a preferred embodiment, the auxiliary agent comprises an anti-settling agent and / or a defoaming agent.

[0029] As a preferred embodiment, the anti-settling agent is bentonite.

[0030] As a preferred embodiment, the defoaming agent is BYK-065 of BYK Company.

[0031] As a preferred embodiment, the mass ratio of the auxiliary agent to the self-polishing polyurethane antifouling resin is 0.1-1:1.

[0032] As a fourth aspect of the application, the application further provides a preparation method of the intrinsic self-polishing polyurethane antifouling paint, comprising: adding the self-polishing resin into an organic solvent, then adding fillers, antifouling agents and auxiliaries, stirring and grinding; and obtaining the intrinsic self-polishing polyurethane antifouling paint after mixing uniformly.

[0033] As a preferred embodiment, the grinding comprises a fineness of 35-60 microns.

[0034] As a fifth aspect of the application, the application further provides an intrinsic self-polishing polyurethane antifouling coating.

[0035] Specifically, the intrinsic self-polishing polyurethane antifouling paint is added into a curing agent, coated on the surface of a base material, and cured at 0-45°C to form a paint film.

[0036] Preferably, the curing agent is hexamethylene diisocyanate.

[0037] As a sixth aspect of the application, the application further provides the application of the above-mentioned intrinsic self-polishing polyurethane antifouling paint or the above-mentioned intrinsic self-polishing polyurethane antifouling coating to the area below the waterline of marine vessels or marine equipment.

[0038] Compared with the prior art, the technical scheme of the application has the beneficial technical effects including:

[0039] 1. The self-polishing polyurethane resin provided by the application has intrinsic antibacterial function. The resin can be slowly and uniformly hydrolyzed in seawater to generate zwitterionic carboxyl betaine functional groups, and the carboxyl betaine has certain antifouling performance.

[0040] 2. The self-polishing polyurethane antifouling resin DEAA-Zn prepared by using the technical scheme of the application is used in combination with antifouling agents, and DEAA-Zn and the antifouling agents can exert synergistic antifouling effect. After being hung in the sea for 12 months in the Ningbo sea area and the Sanya sea area of the East China Sea with higher salinity, the area of marine organisms attached to the surface of the antifouling coating is less than 5%. BRIEF DESCRIPTION OF DRAWINGS

[0041] Figure 1 The synthesis mechanism diagram of the intrinsic self-polishing polyurethane antifouling paint provided for the first embodiment of the application is shown.

[0042] Figure 2 The infrared spectrum diagram of the intrinsic self-polishing polyurethane antifouling paint prepared for the first embodiment of the application is shown. Curve A represents the infrared spectrum of the intermediate acrylic acid-zinc AA-Zn; and curve B represents the infrared spectrum of the self-polishing resin DEAA-Zn.

[0043] Figure 3The photo of the scribe adhesion test is carried out after the intrinsic self-polishing polyurethane antifouling paint prepared in the embodiment 2 of the present application is sprayed on the surface of the carbon steel.

[0044] Figure 4 The photo of the impact resistance test is carried out after the intrinsic self-polishing polyurethane antifouling paint prepared in the embodiment 2 of the present application is sprayed on the surface of the tinplate. DETAILED DESCRIPTION

[0045] In order to make the purpose, technical scheme and advantages of the embodiments of the present application clearer, the technical scheme in the embodiments of the present application will be described clearly and completely below in combination with the embodiments of the present application. Obviously, the described embodiments are part of the embodiments of the present application, rather than all the embodiments of the present application. Based on the embodiments in the present application, all other embodiments obtained by those skilled in the art without creative labor fall within the protection scope of the present application.

[0046] The present application provides a preparation method of an intrinsic self-polishing polyurethane antifouling resin, comprising: preparing an acrylic acid-metal intermediate by reacting acrylic acid, acetic acid and zinc oxide; then generating a self-polishing resin DEAA-Zn containing metal ions and amphoteric ions by addition reaction of the acrylic acid-metal intermediate and diethanolamine, and reacting the DEAA-Zn with HDI to obtain the intrinsic self-polishing polyurethane antifouling resin. The resin DEAA-Zn can be used as the main film-forming material of the antifouling paint.

[0047] In some specific embodiments, the molar ratio of the acrylic acid, acetic acid and zinc oxide is 1:1-1.2:0.8-1.

[0048] In some specific embodiments, the added amount of the mixed solvent is equal to the total mass of the acrylic acid, acetic acid and zinc oxide.

[0049] In some specific embodiments, the xylene and propylene glycol methyl ether acetate are matched in a mass ratio of 1:0.9-1.

[0050] In some specific embodiments, the molar ratio of the added amount of the diethanolamine to the acrylic acid is 1:0.9-1.

[0051] Specifically, the application also provides a preparation method of the intrinsic self-polishing polyurethane antifouling coating, which comprises the following steps: preparing an acrylic acid-zinc (AA-Zn) intermediate by reacting acrylic acid with zinc oxide; then generating a self-polishing resin (DEAA-Zn) by addition reaction of the acrylic acid-zinc intermediate and diethanolamine; and reacting the DEAA-Zn with hexamethylene diisocyanate (HDI) to obtain the intrinsic polyurethane coating. The polyurethane coating can slowly and uniformly hydrolyze into zwitterionic carboxyl betaine in seawater, and the carboxyl betaine has a certain antifouling property. Meanwhile, the DEAA-Zn can be compounded with an antifouling agent, and the antifouling agent is slowly released when the polyurethane coating hydrolyzes, so that the synergistic antifouling effect is achieved.

[0052] More specifically, the preparation steps of the intrinsic self-polishing polyurethane antifouling resin comprise the following steps:

[0053] Firstly, acrylic acid, acetic acid and zinc oxide are mixed in a certain proportion, a mixed solvent of dimethylbenzene and propylene glycol methyl ether acetate is added, and the mixture is stirred at 65-80 °C and 200-300 r / min under the protection of inert argon gas and refluxed for 2-5 h to generate a clear and transparent acrylic acid-metal intermediate.

[0054] Subsequently, the temperature is reduced to 20-35 °C, diethanolamine is slowly added to the acrylic acid-metal intermediate under the protection of argon atmosphere, and then the mixture is stirred at 20-35 °C for 12-24 h to obtain a colorless and transparent self-polishing polyurethane antifouling resin DEAA-Zn.

[0055] The intrinsic self-polishing polyurethane antifouling coating provided by the application is prepared from the self-polishing resin DEAA-Zn.

[0056] In some specific embodiments, the intrinsic self-polishing polyurethane antifouling coating comprises the following raw materials in mass parts: 15-25 parts of the self-polishing resin DEAA-Zn, 15-30 parts of an antifouling agent, 10-20 parts of a filler, 20-30 parts of an organic solvent and 1.5-2.5 parts of an additive.

[0057] In some specific embodiments, the antifouling agent comprises a combination of cuprous oxide and zineb.

[0058] In some specific embodiments, the filler is selected from a combination of one or more of red iron oxide, barium sulfate and talcum powder.

[0059] In some specific embodiments, the additive is selected from one or a combination of several anti-settling agents or defoaming agents.

[0060] In some specific embodiments, the anti-settling agent is bentonite.

[0061] In some specific embodiments, the defoaming agent is BYK-065 of BYK Company.

[0062] In some specific embodiments, the self-polishing polyurethane antifouling paint further comprises a curing agent, which is mixed with all the components including the self-polishing polyurethane antifouling resin DEAA-Zn before use, and the self-polishing polyurethane antifouling paint is obtained after uniform stirring and aging.

[0063] The application provides a preparation method of the self-polishing polyurethane antifouling paint, specifically: the self-polishing polyurethane antifouling resin DEAA-Zn is dissolved in an organic solvent, then an antifouling agent, a filler and an additive are sequentially added, stirring is performed at 1500 / min for 20 min, grinding is performed to a fineness of 35-60 microns, and packaging is performed.

[0064] The self-polishing polyurethane antifouling paint prepared by compounding the antifouling agent in the self-polishing resin DEAA-Zn can synergistically improve the static antifouling efficiency of the coating.

[0065] The application further provides a self-polishing polyurethane antifouling coating, which is obtained by mixing the self-polishing polyurethane antifouling resin DEAA-Zn with a curing agent HDI, and then performing a curing reaction at room temperature to 45 DEG C to form a paint film on the surface of a base material.

[0066] Preferably, the curing agent is hexamethylene diisocyanate curing agent 30-40 parts.

[0067] When the antifouling paint is used in a seawater environment, the antifouling paint can slowly and uniformly hydrolyze in seawater to generate an amphoteric ionic carboxyl betaine functional group with antifouling performance.

[0068] The application further provides an application of the self-polishing polyurethane antifouling paint, which is used for marine equipment protection, including protection of ships and marine platforms.

[0069] The application provides an application of the self-polishing polyurethane antifouling paint in marine equipment protection, including marine ships and marine platforms, and especially the application in the region below the waterline of marine equipment.

[0070] In the following examples, the test materials and reagents used, unless otherwise specified, can be obtained from commercial channels.

[0071] In the examples, the specific techniques or conditions not specified are all performed according to the techniques or conditions described in the literature in the field or according to the product instructions.

[0072] Example 1

[0073] The embodiment provides an intrinsic self-polishing polyurethane antifouling paint and a preparation method, antifouling paint preparation and application thereof, and the specific preparation steps comprise the following steps:

[0074] 1) Preparation of the intrinsic self-polishing polyurethane antifouling paint

[0075] Referring to Figure 1 , the reaction formula 1 and the reaction formula 2 are principle schematic diagrams for preparing the intrinsic self-polishing resin DEAA-Zn.

[0076] Specifically, the preparation steps of the self-polishing polyurethane antifouling paint comprise the following steps: 1 mol of acrylic acid, 1 mol of acetic acid and 0.9 mol of zinc oxide are weighed and added into a three-necked flask, 135 g of dimethylbenzene and 135 g of propylene glycol methyl ether acetate are added into the three-necked flask, under an argon atmosphere, 70 DEG C, 300 r / min stirring reflux is carried out for 2 h, and then a clear and transparent intermediate acrylic acid-zinc (AA-Zn, details are shown in the reaction formula 1) can be generated. Figure 1 The infrared spectrum diagram of the reaction formula 1 is shown in Figure 2 - curve A. Subsequently, the temperature is reduced to 25 DEG C, 1 mol of diethanolamine is slowly added into the above AA-Zn under an argon atmosphere, and then 35 DEG C stirring is carried out for 12 h, and then a colorless and transparent self-polishing resin DEAA-Zn (details are shown in the reaction formula 2) is obtained. Figure 1 The infrared spectrum diagram of the reaction formula 2 is shown in Figure 2 - curve B.

[0077] Referring to Figure 2 , the absorption peaks at 1436 cm -1 and 1535 cm -1 correspond to the symmetric stretching vibration and asymmetric stretching vibration absorption peaks of a typical zinc carboxylate (-COO-Zn 2+ ) respectively; 1649 cm -1 is the stretching vibration absorption peak of a C=C double bond; the absorption peaks at 2800~3000 cm -1 correspond to the stretching vibration absorption peaks of C-H bonds; Figure 2 , the stretching vibration absorption peak of the C=C double bond 1649 cm -1 disappears, and a C-N stretching vibration absorption peak is newly generated at 1056 cm -1 . The infrared result shows that the diethanolamine and the zinc acrylic resin undergo an addition reaction, the C=C double bond disappears, and the self-polishing resin DEAA-Zn is generated.

[0078] 2) Preparation of the antifouling paint:

[0079] To the 25g self-polishing resin DEAA-Zn prepared in step 1), 15g cuprous oxide, 10g Zineb (zinc ethylene bisdithiocarbamate) were added, stirred at 500r / min for 5min, then 5g red iron oxide and 10g talc were added, stirred uniformly, then 10g xylene and 10g ethyl acetate were added, 0.5g BYK-065 as defoaming agent and 1.5g bentonite as anti-settling agent were added, stirred at 2000r / min for 30min, ground to a paint fineness of 40μm, finally 35g curing agent HDI (Chinese name: hexamethylene diisocyanate, purchased from Covestro, brand Desmodur H) was added, stirred uniformly, aged for 5min, to obtain the antifouling coating.

[0080] Referring to the reaction formula ③ in Figure 1 , it is a schematic diagram of the reaction principle of self-polishing resin DEAA-Zn and hexamethylene diisocyanate HDI, DEAA-Zn and HDI undergo polymerization to produce polyurethane, forming a polyurethane antifouling coating.

[0081] Referring to the reaction formula ④ in Figure 1 , it is the hydrolysis of the polyurethane antifouling coating in seawater to generate amphoteric zwitterionic carboxybetaine with antifouling properties.

[0082] The antifouling coating prepared in Example 1 was sprayed onto a carbon steel plate (the size of the carbon steel plate was 350×250×3mm, the substrate was first sandblasted to Sa2.5 level, then coated with an epoxy anticorrosive primer with a dry film thickness of 80μm) using compressed air, and cured at room temperature 25℃ for 24h, the antifouling paint film thickness was controlled at 80±2μm, to obtain the antifouling coating test plate. The antifouling test plate was subjected to static hanging plate test in Sanya sea area and East China Ningbo sea area according to the method of “GBT 5370-2007 Antifouling paint sample plate shallow sea immersion test method”, and the antifouling effect after 12 months is shown in Table 1.

[0083] Example 2

[0084] This example provides an intrinsic self-polishing polyurethane antifouling coating, the preparation method is basically the same as that of Example 1, the difference is only that 15g cuprous oxide and 15g Zineb are added during the preparation of the antifouling coating, and the amount of talc added is adjusted to 5g. The others are the same.

[0085] The antifouling coating test plate prepared in this example 2 was subjected to static antifouling hanging plate test in Sanya sea area and East China Ningbo sea area, and the antifouling effect after 12 months is shown in Table 1.

[0086] The coating prepared in the example was sprayed on the surface of carbon steel, and the crosshatch adhesion test and impact resistance test were carried out, and the test results are shown in Figure 3 and Figure 4 .

[0087] Referring to Figure 3 , is the photo of the anti-fouling paint prepared in this example sprayed on the tinplate for the anti-fouling paint impact resistance test. The impact area is observed with a 4x magnifying lens, and the paint film is complete, without damage or cracks, indicating good impact resistance on the tinplate.

[0088] Referring to Figure 4 , is the photo of the cross-hatch adhesion test of the coating formed by spraying the anti-fouling paint prepared in this example on the carbon steel plate. The paint film at the scribed line is not collapsed or peeled off, and the cross-hatch adhesion test is 0 grade, indicating good bonding performance of the coating on the carbon steel plate.

[0089] Example 3

[0090] This example provides an intrinsic self-polishing polyurethane anti-fouling paint and its preparation method, anti-fouling paint preparation and application. The preparation method is basically the same as that of Example 1, except that the anti-fouling agent in the anti-fouling paint in step 2) is different. The comparative example includes: adding 15g cuprous oxide and 5g zineb to the 25g self-polishing resin DEAA-Zn prepared in step 1), and adjusting the amount of talc added to 15g, and the others are the same.

[0091] Comparative Example 1

[0092] This comparative example provides an intrinsic self-polishing polyurethane anti-fouling paint and its preparation method, anti-fouling paint preparation and application. The preparation method is basically the same as that of Example 1, except that no anti-fouling agent is added, and 40g red iron oxide and 10g talc are added, and the other steps are the same.

[0093] The anti-fouling coating test panel prepared in Comparative Example 1 was subjected to static anti-fouling hanging test in Sanya sea area and East China Ningbo sea area, and the anti-fouling effect after 12 months is shown in Table 1.

[0094] Comparative Example 2

[0095] This comparative example provides an intrinsic self-polishing polyurethane anti-fouling paint and its preparation method, anti-fouling paint preparation and application. The preparation method is basically the same as that of Example 1, except that 25g of commercially available acrylic resin is used instead of 25g of intrinsic polyurethane anti-fouling coating, and the other steps are the same.

[0096] The anti-fouling coating test panel prepared in Comparative Example 2 was subjected to static anti-fouling hanging test in Sanya sea area and East China Ningbo sea area, and the anti-fouling effect after 12 months is shown in Table 1.

[0097] Comparative Example 3

[0098] The comparative example 2 provides a kind of intrinsic self-polishing polyurethane antifouling coating and its preparation method, antifouling coating preparation and application, its preparation method is basically same with example 1, the difference is only in: using 25g of commercially available acrylic resin instead of 25g intrinsic polyurethane antifouling coating, also no antifouling agent is added, 40g of red iron oxide and 10g of talc powder are added, other steps are same.

[0099] The antifouling coating test panel prepared by comparative example 3 is subjected to static antifouling hanging panel test in Sanya sea area and East China Sea Ningbo sea area respectively, and the antifouling effect after 12 months is shown in Table 1.

[0100] Comparative example 4

[0101] The comparative example 2 provides a kind of intrinsic self-polishing polyurethane antifouling coating and its preparation method, antifouling coating preparation and application, its preparation method is basically same with example 1, the difference is only in: the preparation step of intrinsic self-polishing polyurethane antifouling coating in step 1) is different.

[0102] In the comparative example, the preparation step of self-polishing polyurethane antifouling coating includes: 2mol acetic acid, 0.9mol zinc oxide is added to a three-necked flask, 135g of dimethylbenzene and 135g of propylene glycol methyl ether acetate are added to the three-necked flask, under argon atmosphere, at 70℃, 300r / min stirring reflux 2h. Other steps are same.

[0103] The self-polishing resin DEAA-Zn obtained in the comparative example is reacted with the curing agent HDI to form a coating, but it cannot form a film, and the antifouling topcoat has no adhesion on the epoxy anticorrosive primer of the carbon steel substrate antifouling test panel, so it cannot be subjected to antifouling test in seawater.

[0104] Comparative example 5

[0105] The comparative example 2 provides a kind of intrinsic self-polishing polyurethane antifouling coating and its preparation method, antifouling coating preparation and application, its preparation method is basically same with example 1, the difference is only in: the antifouling agent in antifouling coating in step 2) is different, the comparative example includes: 15g cuprous oxide and 15g zinc pyrithione are added to 25g self-polishing resin DEAA-Zn prepared in step 1), talc powder is 5g, others are same.

[0106] Comparative example 6

[0107] The comparative example provides an intrinsic self-polishing polyurethane antifouling coating and a preparation method thereof, antifouling coating preparation and application, the preparation method is basically the same as that of example 1, the difference is only that the antifouling agent in the antifouling coating in step 2) is different, the comparative example includes: 15g cuprous oxide and 5g zinc pyrithione are added to the 25g self-polishing resin DEAA-Zn prepared in step 1), and then 15g talc powder is added, and the other steps are the same.

[0108] As can be seen from Table 1, the antifouling coating prepared by example 1- example 3, after 12 months of antifouling panel test in high salinity seawater area, the marine organism attachment area of the antifouling paint panel is less than 5%, which shows that the self-polishing polyurethane antifouling resin provided by the application is compounded with the antifouling agent to prepare the antifouling coating, which shows good antifouling performance in static East China Ningbo sea area (average salinity is 30‰) and Sanya sea area (average salinity is 35‰), among which the marine organism attachment area of the antifouling coating of example 2 is the least, which shows that the antifouling performance of the mass ratio of zineb to cuprous oxide at 1:1 is the best; Especially, after 12 months of continuous hanging, the surface of the antifouling coating prepared by example 1- example 3 does not appear phenomena such as blistering and falling off, obviously, the long-term use of the antifouling coating in high salinity seawater area shows obvious advantages of salt resistance and pollution resistance.

[0109] Further comparison of the test results of example 1 and comparative example 1 shows that the polyurethane antifouling coating prepared by comparative example 1 has partial antifouling effect after 12 months of hanging in East China Ningbo sea area and Sanya sea area, but the antifouling effect cannot meet the use requirements in seawater, only the antifouling coating prepared by compounding the self-polishing polyurethane antifouling resin provided by the application with the antifouling agent can have good antifouling performance.

[0110] By comparing the test results of example 1 and comparative example 2, when the main film-forming material (polyurethane resin) of the intrinsic self-polishing polyurethane antifouling coating does not have hydrolysis self-polishing performance, the antifouling agent cannot be released in the resin, and the antifouling performance of the antifouling agent is greatly weakened.

[0111] By comparing the test results of example 1, comparative example 2 and comparative example 3, the intrinsic self-polishing polyurethane antifouling coating prepared by example 1 can achieve synergistic antifouling effect in seawater immersion area by compounding with the antifouling agent; the main principle includes: the polyurethane antifouling coating can be slowly and uniformly hydrolyzed in seawater to generate amphoteric ionic carboxyl betaine functional groups, the carboxyl betaine functional groups themselves have certain antifouling function, especially, the self-polishing polyurethane antifouling resin can release the antifouling agent in the coating during the hydrolysis process, which synergistically kills the marine organisms attached to the surface of the paint film; obviously, by using the technical scheme of the application, the self-polishing polyurethane antifouling resin DEAA-Zn synergistically acts with the antifouling agent, which significantly improves the antifouling performance of the intrinsic self-polishing polyurethane antifouling coating.

[0112] Table 1 Effect comparison of antifouling coatings of examples and comparative examples

[0113]

[0114] By comparing the test results of Example 2 and Comparative Example 5, it is shown that the antifouling performance of Zineb is more excellent than that of zinc pyrithione, and in terms of cost, the market prices of the two are about 160 yuan / kg for zinc pyrithione and about 80 yuan / kg for Zineb. Obviously, in the case of mass production of self-polishing polyurethane antifouling coatings, the price of zinc pyrithione is much higher than that of Zineb, which significantly increases the cost of antifouling coatings. The test results of Example 3 and Comparative Example 6 show that when used in combination with cuprous oxide, the antifouling performance of Zineb is better than that of zinc pyrithione, and without adding Zineb, the antifouling performance of self-made self-polishing polyurethane antifouling coatings will be significantly reduced, which shows that the synergistic antifouling effect of Zineb combined with cuprous oxide is better than that of zinc pyrithione combined with cuprous oxide. By comparing Example 2 and Comparative Examples 5-6, it is known that the use of Zineb instead of an equal amount of zinc pyrithione can not only achieve better antifouling effect, but also greatly reduce the preparation cost.

[0115] The above description of the examples is to facilitate the understanding and use of the invention by those of ordinary skill in the art. Those skilled in the art can easily make various modifications to these examples and apply the general principles described herein to other examples without creative labor. Therefore, the present application is not limited to the above examples, and improvements and modifications made by those skilled in the art without departing from the scope of the present application should be within the scope of the present application.

Claims

1. An intrinsic self-polishing polyurethane antifouling coating, comprising a paint film formed after a curing agent is added to an intrinsic self-polishing polyurethane antifouling coating, and the intrinsic self-polishing polyurethane antifouling coating is coated on a surface of a base material and cured at room temperature to 45℃. The components of the intrinsic self-polishing polyurethane antifouling coating include, by mass fraction, 15-25 parts of a self-polishing polyurethane antifouling resin precursor, 15-30 parts of an antifouling agent, 10-20 parts of a filler, and 20-30 parts of an organic solvent. The self-polishing polyurethane antifouling resin precursor is prepared by an addition reaction of a zinc carboxylate intermediate and a diol amine. The zinc carboxylate intermediate is a zinc carboxylate salt containing a terminal carboxyl group. The zinc carboxylate intermediate is obtained by a neutralization reaction of a first carboxylic acid monomer, a second carboxylic acid monomer, and zinc oxide. The first carboxylic acid monomer is any one of acrylic acid and methacrylic acid. The second carboxylic acid monomer is any one of acetic acid, propionic acid, and n-butyric acid. The curing agent is hexamethylene diisocyanate. The molar ratio of the first carboxylic acid monomer, the second carboxylic acid monomer, and zinc oxide is 1:1-1.2:0.8-1. The molar ratio of the zinc carboxylate intermediate and the diol amine is 1:0.9-1. The diol amine is diethanolamine.

2. The intrinsic self-polishing polyurethane antifouling coating according to claim 1, characterized in that, The neutralization reaction includes adding the first carboxylic acid monomer, the second carboxylic acid monomer, and zinc oxide to a reaction solvent, stirring at 200-300 r / min under reflux at 65-80℃ for 2-5 h under inert gas protection.

3. The intrinsic self-polishing polyurethane antifouling coating according to claim 2, characterized in that, The reaction solvent is a mixed solvent of xylene and propylene glycol methyl ether acetate.

4. The intrinsic self-polishing polyurethane antifouling coating according to claim 3, characterized in that, The mass ratio of xylene to propylene glycol methyl ether acetate is 1:0.9-1.

5. The intrinsic self-polishing polyurethane antifouling coating according to claim 2, characterized in that, The inert gas is argon.

6. The intrinsic self-polishing polyurethane antifouling coating according to claim 1, characterized in that, The conditions of the addition reaction include reducing the temperature to 20-35℃, adding the diol amine dropwise to the zinc carboxylate intermediate under inert gas protection, and stirring for 20-24 h to obtain the self-polishing polyurethane antifouling resin precursor.

7. The intrinsic self-polishing polyurethane antifouling coating according to claim 1, characterized in that, The organic solvent is xylene or ethyl acetate.

8. The intrinsic self-polishing polyurethane antifouling coating according to claim 1, characterized in that, The filler is selected from a combination of one or more of iron oxide, barium sulfate, and talc.

9. The intrinsic self-polishing polyurethane antifouling coating according to claim 1, characterized in that, The antifouling agent includes a combination of cuprous oxide and zineb.

10. The intrinsic self-polishing polyurethane antifouling coating according to claim 9, characterized in that, The mass ratio of cuprous oxide to zineb is 1:1-3:

1.

11. The intrinsically self-polishing polyurethane antifouling coating according to claim 1, characterized in that, The mass ratio of the antifouling agent to the self-polishing polyurethane antifouling resin precursor is 1-2:

1.

12. The intrinsic self-polishing polyurethane antifouling coating according to any one of claims 1 to 11, characterized in that, The components of the intrinsic self-polishing polyurethane antifouling coating further include an auxiliary agent. The auxiliary agent includes an anti-settling agent and / or a defoaming agent.

13. The intrinsic self-polishing polyurethane antifouling coating according to claim 12, characterized in that, The anti-settling agent is bentonite. The defoaming agent is BYK-065 from BYK.

14. The intrinsic self-polishing polyurethane antifouling coating according to claim 12, characterized in that, The preparation method of the intrinsic self-polishing polyurethane antifouling coating includes adding the self-polishing polyurethane antifouling resin precursor to an organic solvent, then adding a filler, an antifouling agent, and an auxiliary agent, stirring, and grinding to obtain the intrinsic self-polishing polyurethane antifouling coating. The grinding includes a fineness of 35-60 microns.

15. Use of the intrinsic self-polishing polyurethane antifouling coating according to any one of claims 1-14 in marine vessels or marine equipment.

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