A temperature-controlled release and degradation antifouling coating and preparation method thereof

Abstract

The present invention relates to the field of chemical materials technology. It provides a temperature-controlled release degradable antifouling coating and a preparation method. The antifouling coating comprises: component A, comprising a polyhydroxy degradable polyester copolymer, a temperature-sensitive resin polymer, a composite antifouling agent, a temperature-sensitive gel-coated antifouling agent, an auxiliary antifouling agent, a defoaming agent, a pigment, a filler, an anti-settling agent, and a first solvent; and component B, comprising a polyisocyanate and a second solvent. The mass ratio of component A to component B is 10:0.9-1.2. The temperature-controlled release degradable antifouling coating of the present invention utilizes a composite resin base of a degradable polyhydroxy degradable polyester copolymer and a temperature-sensitive resin polymer, and simultaneously composites the temperature-sensitive gel-coated antifouling agent. The resulting antifouling coating not only achieves high antifouling effectiveness in waters of varying temperatures but also possesses the degradation properties of a degradable antifouling coating, maintaining excellent antifouling effectiveness even when moored.

Description

Technical Field

[0001] The present invention relates to the technical field of chemical materials, and in particular to an antifouling coating capable of temperature-controlled release and degradation and a preparation method thereof. Background Art

[0002] At present, marine biofouling is still a major bottleneck problem for global shipping, resulting in a surge in navigation resistance and excessive fuel consumption. The current antifouling coatings are mainly self-polishing, releasing antifouling agents through the action of water scouring. The antifouling effect is more obvious when sailing, but there is also the problem of excessive release of internal antifouling agents during long-term water scouring. In addition, this type of antifouling coating cannot intelligently control the release of antifouling agents according to temperature changes when moored, resulting in limited antifouling effects in high-temperature sea areas where fouling organisms are active, making it difficult to achieve long-term antifouling in multiple sea areas. Therefore, achieving temperature-controlled release and controllable degradation of the coating to control the consumption rate of the antifouling agent, so that it can maintain an appropriate antifouling concentration on the surface without excessive consumption when marine organisms grow slowly at room temperature and low temperature, and can control the release of more antifouling agents in high-temperature sea areas to adapt to environmental changes, is the key to achieving long-term antifouling.

[0003] Research on degradable antifouling coatings is increasing in China. Patent application number CN201610682362.2 discloses a method for preparing a degradable antifouling resin and its use, including: synthesizing a degradable polylactic acid block polymer P1, whose raw materials are lactic acid, a polyol and / or polyester polyol, a catalyst, and solvent A; synthesizing a polylactic acid block polymer-based acrylate P2, whose raw materials are P1, triethylamine, methacryloyl chloride, and solvent B; and synthesizing a degradable acrylate polymer P3, whose raw materials are P2, a methacrylate monomer, an initiator, and solvent C. While the degradable antifouling resin prepared in this patent can be used in the preparation of degradable antifouling coatings, and the resulting antifouling coatings exhibit excellent resistance to seawater immersion and controllable degradation, thereby controlling the release of the antifouling agent and achieving long-term antifouling effects, the antifouling coatings are not temperature-sensitive, and their effectiveness in high-temperature waters is limited.

[0004] Patent application number CN202080005835.X discloses a solvent-free marine antifouling coating and its preparation method. This coating utilizes a combination of degradable polyester polyols and castor oil derivatives to adjust the coating's crosslinking density and speed, as well as the viscosity of the coating system. It eliminates the need for organic solvents and is environmentally friendly. The prepared antifouling coating demonstrates good performance after one year of shallow sea immersion. While this patent demonstrates good antifouling effectiveness, the coating lacks temperature sensitivity, limiting its effectiveness in high-temperature waters.

[0005] Therefore, while the applicant is researching degradable antifouling coatings, it is also committed to researching temperature-responsive antifouling compositions that adjust the release rate of antifouling agents when seawater temperature changes. Patents have been applied for before. For example, the patent application document with Chinese patent application number CN201911104831.2 discloses an antifouling coating with seawater temperature response function. The antifouling coating uses a self-polishing resin and a thermosensitive resin as a resin base material. The prepared antifouling coating not only has the polishing performance of a self-polishing antifouling coating, but also has the characteristics of responding to seawater temperature. The thermosensitive resin is hydrophilic at low temperature, the chain segments open, and hydrophobic at high temperature, and the chain segments shrink. The antifouling coating can achieve controlled release of antifouling agents under different seawater temperature conditions, improve the use efficiency of antifouling agents, and extend the antifouling period. However, since the main resin compounded with the thermosensitive resin in this patent is a self-polishing resin, there is a bottleneck that the self-polishing antifouling coating needs to rely on water flow to release the antifouling agent, and cannot effectively prevent fouling when moored. Therefore, how to improve the antifouling ability of antifouling coatings when moored and apply temperature-responsive compositions to antifouling coatings to achieve high antifouling effects in waters of different temperatures has been a topic that the inventors have been studying since then.

[0006] Therefore, how to develop a seawater temperature-responsive, degradable antifouling coating with excellent performance is not only a research topic that the inventors are committed to researching, but also a problem that urgently needs to be solved in the field of ship antifouling coatings.

[0007] In view of this, the present invention is proposed. Summary of the Invention

[0008] The purpose of the present invention is to provide an antifouling coating with temperature-controlled release and degradation and a preparation method, so as to solve the problem in the prior art of how to achieve high antifouling effect in sea areas with different temperatures without relying on water flow to release antifouling agents, and to achieve high antifouling effect even when moored.

[0009] To achieve the above object, the technical solution of the present invention is achieved as follows:

[0010] A temperature-controlled release and degradation antifouling coating, comprising:

[0011] Component A, comprising a polyhydroxy degradable polyester copolymer, a temperature-sensitive resin polymer, a composite antifouling agent, a temperature-sensitive gel-coated antifouling agent, an auxiliary antifouling agent, a defoaming agent, a pigment and filler, an anti-settling agent, and a first solvent;

[0012] Component B, comprising a polyisocyanate and a second solvent;

[0013] The mass ratio of component A to component B is 10:0.9-1.2.

[0014] Furthermore, the component A comprises the following components in parts by mass: 15-25 parts of a polyhydroxy degradable polyester copolymer, 3-10 parts of a temperature-sensitive resin polymer, 50-60 parts of a composite antifouling agent, 1-3 parts of a temperature-sensitive gel-coated antifouling agent, 4-10 parts of an auxiliary antifouling agent, 0.5-1 part of a defoaming agent, 1-5 parts of a pigment and filler, 0.5-1 part of an anti-settling agent, and 4-6 parts of a first solvent;

[0015] The component B includes the following components in parts by mass: 2.5 to 4 parts of polyisocyanate and 6.5 to 8 parts of a second solvent.

[0016] Furthermore, the polyhydroxy degradable polyester copolymer is a copolymer prepared by polymerization of at least one monomer selected from lactide, valerolactone, caprolactone, lactic acid, and glycolic acid under the initiation of ethyl butyl propylene glycol.

[0017] Furthermore, the temperature-sensitive resin polymer is a polymer formed by free radical copolymerization of a temperature-sensitive monomer, a hydroxy acrylic resin, and a fluorine-containing acrylic resin monomer under the action of an initiator.

[0018] Furthermore, the composite antifouling agent includes a first component and a second component, the first component is at least one of bromopyrrolecarbonitrile, copper pyrithione, zinc pyrithione, medetomidine and 4,5-dichloro-2-n-octyl-3-isothiazolinone, and the second component is cuprous oxide.

[0019] Furthermore, the thermosensitive gel-coated antifouling agent is a thermosensitive gel-coated at least one of bromopyrrole carbonitrile, capsaicin and diterpene carboxamide compounds.

[0020] Furthermore, the auxiliary antifouling agent is primary zinc oxide.

[0021] Furthermore, the polyisocyanate is at least one of polyisocyanate N3390, polyisocyanate N75 or polyisocyanate L75.

[0022] Furthermore, the first solvent and the second solvent are at least one of xylene and ethyl acetate.

[0023] In a second aspect of the present invention, a method for preparing a temperature-controlled release degradable antifouling coating is provided. The method for preparing a temperature-controlled release degradable antifouling coating is used to prepare any one of the above-mentioned temperature-controlled release degradable antifouling coatings, and the preparation method comprises the following steps:

[0024] S1. Preparation of component A: uniformly disperse the polyhydroxy degradable polyester copolymer, the temperature-sensitive resin polymer, 70% by mass of the defoamer, the anti-settling agent, and the first solvent at high speed according to the mass ratio, then add the first component of the composite antifouling agent, the temperature-sensitive gel-coated antifouling agent, the auxiliary antifouling agent, and the pigment and filler, and uniformly disperse them; then add the second component of the composite antifouling agent and 30% by mass of the defoamer, uniformly disperse them, and then sand grind them to obtain component A;

[0025] S2. Preparation of component B: uniformly disperse the polyisocyanate and the second solvent according to the mass ratio to obtain component B;

[0026] S3. Preparation of antifouling coating: uniformly mixing component A and component B at a mass ratio of 10:0.9-1.2 to obtain the temperature-controlled release and degradation antifouling coating.

[0027] Compared with the prior art, the temperature-controlled release and degradation antifouling coating and preparation method of the present invention have the following beneficial effects:

[0028] The present invention discloses a temperature-controlled release degradation antifouling coating and its preparation method. The coating adopts a compound of a degradable resin polyhydroxy degradable polyester copolymer and a thermosensitive resin thermosensitive resin polymer as the resin base material, and simultaneously compounds a thermosensitive gel to coat the antifouling agent. The prepared antifouling coating not only has the degradation performance of the degradable antifouling coating, but also does not need to rely on water flow to release the antifouling agent. It still has an excellent antifouling effect when moored. At the same time, it has the characteristics of responding to seawater temperature. By utilizing the temperature-sensitive properties of the thermosensitive resin and the coating, the antifouling coating can achieve the controlled release of the antifouling agent under different seawater temperature conditions, improve the use efficiency of the antifouling agent, and extend the antifouling effect. In addition, the coating has excellent mechanical properties and supporting properties, and has a wide range of application scenarios. Furthermore, the raw materials for the preparation of the antifouling coating are abundant, low-priced, and the synthesis process is simple. It takes into account both product performance and cost control issues, has good economic value, and is expected to replace the conventional antifouling coatings currently used in the market in the future, with broad market prospects. BRIEF DESCRIPTION OF THE DRAWINGS

[0029] Figure 1 This is a schematic diagram of the copper ion leakage rate of a temperature-controlled release and degradable antifouling coating according to an embodiment of the present invention under different seawater temperature conditions;

[0030] Figure 2 This is a schematic diagram of the test results of a temperature-controlled release degradation antifouling coating according to an embodiment of the present invention applied on a panel and immersed in the shallow waters of Sanya for three years;

[0031] Figure 3 This is a schematic diagram of the test results of a temperature-controlled release degradation antifouling coating according to an embodiment of the present invention applied on a panel and immersed in the shallow waters of Xiamen for three years;

[0032] Figure 4 This is a schematic diagram of adhesion test results of an antifouling coating capable of temperature-controlled release of degradation according to an embodiment of the present invention applied on a panel. DETAILED DESCRIPTION

[0033] It should be noted that, in the absence of conflict, the embodiments of the present invention and the features in the embodiments can be combined with each other. The descriptions of "first", "second", etc. mentioned in the embodiments of the present invention are only for descriptive purposes and cannot be understood as indicating or implying their relative importance or implicitly indicating the number of technical features indicated. Therefore, the features defined as "first" and "second" may explicitly or implicitly include at least one of the features. In addition, the technical solutions between the various embodiments can be combined with each other, but they must be based on the ability of ordinary technicians in this field to implement them. When the combination of technical solutions is contradictory or cannot be implemented, it should be deemed that such a combination of technical solutions does not exist and is not within the scope of protection required by the present invention.

[0034] The present invention will be described in detail below with reference to the accompanying drawings and in conjunction with embodiments.

[0035] The problem in the existing technology is how to achieve high antifouling effect in sea areas with different temperatures without relying on water flow to release antifouling agents, and how to achieve high antifouling effect even when anchored.

[0036] In order to solve the above problems, the present invention provides a temperature-controlled release degradable antifouling coating, the temperature-controlled release degradable antifouling coating comprising:

[0037] Component A, comprising a polyhydroxy degradable polyester copolymer, a temperature-sensitive resin polymer, a composite antifouling agent, a temperature-sensitive gel-coated antifouling agent, an auxiliary antifouling agent, a defoaming agent, a pigment and filler, an anti-settling agent, and a first solvent;

[0038] Component B includes polyisocyanate and a second solvent.

[0039] The mass ratio of component A to component B is 10:0.9-1.2.

[0040] Specifically, the component A includes the following raw materials in parts by weight: 15-25 parts of a polyhydroxy degradable polyester copolymer, 3-10 parts of a temperature-sensitive resin polymer, 50-60 parts of a composite antifouling agent, 1-3 parts of a temperature-sensitive gel-coated antifouling agent, 4-10 parts of an auxiliary antifouling agent, 0.5-1 part of a defoaming agent, 1-5 parts of a pigment and filler, 0.5-1 part of an anti-settling agent, and 4-6 parts of a first solvent;

[0041] The component B comprises the following raw materials in parts by weight: 2.5 to 4 parts of polyisocyanate and 6.5 to 8 parts of a second solvent.

[0042] Specifically, the polyhydroxy degradable polyester copolymer is a copolymer prepared by polymerization of at least one monomer selected from lactide, valerolactone, caprolactone, lactic acid, and glycolic acid under the initiation of ethyl butyl propylene glycol, and has a molecular weight of 2000 to 4000.

[0043] Specifically, the temperature-sensitive resin polymer is a polymer formed by free radical copolymerization of a temperature-sensitive monomer, a hydroxyl acrylic resin, and a fluorine-containing acrylic resin monomer under the action of an initiator, and has a molecular weight of 4,000 to 20,000.

[0044] More specifically, the temperature-sensitive monomer is N-isopropylacrylamide.

[0045] More specifically, the hydroxy acrylic resin is at least one of ethyl hydroxy acrylate and butyl hydroxy acrylate.

[0046] More specifically, the fluorine-containing acrylic resin monomer is at least one of trifluoroethyl methacrylate and hexafluorobutyl acrylate.

[0047] More specifically, the initiator is at least one of dibenzoyl peroxide (BPO) and azobisisobutyronitrile (AIBN).

[0048] More specifically, the preparation method of the temperature-sensitive resin polymer includes the following steps: adding 40 to 50 parts of a third solvent, 30 to 40 parts of a temperature-sensitive monomer, 2 to 5 parts of a hydroxyl acrylic resin, and 2 to 5 parts of a fluorine-containing acrylic resin into a reactor, heating the reactor to 80 to 90°C, dissolving 0.5 to 1 part of an initiator in 10 parts of the third solvent, and adding the initiator dropwise to the reactor for 2 to 3 hours. After the initiator is added dropwise, the temperature is controlled to rise to 90 to 100°C and the reaction is continued for 6 hours, and then the material is cooled and discharged.

[0049] Dissolving the initiator in a third solvent before slowly adding it dropwise to the reactor allows for precise control of the initiator concentration and reaction rate. This prevents local overheating and runaway reactions caused by adding too much initiator at once. It also ensures a more even distribution of the initiator throughout the reaction system, thereby improving polymer uniformity and performance.

[0050] Raise the temperature to 80-90°C and begin adding the initiator dropwise. After the addition is complete, continue the reaction at 90-100°C for 6 hours. This temperature range is usually determined based on the polymerization characteristics of the selected monomers to ensure smooth polymerization while avoiding side reactions and polymer degradation caused by excessively high temperatures.

[0051] After the initiator is added, the reaction is continued for 6 hours to ensure that the monomers are fully polymerized to form a high molecular weight temperature-sensitive resin polymer. Too short a reaction time may result in insufficient monomer conversion, while too long a reaction time may induce unnecessary side reactions.

[0052] The temperature-sensitive resin polymer prepared by the above-mentioned preparation method of the temperature-sensitive resin polymer not only gives the antifouling coating a controlled release effect on the antifouling agent under different seawater temperature conditions, thereby improving the antifouling effect in high-temperature sea areas and the utilization efficiency of the antifouling agent in low-temperature sea areas; it also improves the overall smoothness and surface state of the coating, which has a positive effect on the antifouling effect of the coating; in addition, it also improves the adhesion of the coating.

[0053] The third solvent is at least one of xylene and cyclohexanone.

[0054] Specifically, the composite antifouling agent includes a first component and a second component, the first component is at least one of bromopyrrolecarbonitrile, copper pyrithione, zinc pyrithione, medetomidine and 4,5-dichloro-2-n-octyl-3-isothiazolinone, and the second component is cuprous oxide.

[0055] Specifically, the thermosensitive gel-coated antifouling agent is a thermosensitive gel-coated at least one of bromopyrrole carbonitrile, capsaicin and diterpene carboxamide compounds.

[0056] Specifically, the auxiliary antifouling agent is primary zinc oxide.

[0057] Specifically, the defoaming agent is at least one of defoaming agent 6600 and YRXP-06.

[0058] Specifically, the pigment and filler is at least one of talc powder and barite powder.

[0059] Specifically, the anti-settling agent is a slurry made of polyamide wax powder and xylene.

[0060] Specifically, the first solvent and the second solvent are at least one of xylene and ethyl acetate.

[0061] Specifically, the polyisocyanate is at least one of polyisocyanate N3390, polyisocyanate N75 or polyisocyanate L75.

[0062] In a second aspect of the present invention, a method for preparing a temperature-controlled release degradable antifouling coating is provided. The method for preparing a temperature-controlled release degradable antifouling coating is used to prepare any one of the above-mentioned temperature-controlled release degradable antifouling coatings, and the preparation method comprises the following steps:

[0063] S1. Preparation of component A: Add polyhydroxy degradable polyester copolymer, thermosensitive resin polymer, 70% of the mass of defoamer, anti-settling agent and first solvent into a pull cylinder according to mass ratio, mix and disperse evenly at high speed to form a basic coating matrix; then add the first component of composite antifouling agent, thermosensitive gel-coated antifouling agent, auxiliary antifouling agent and pigment and filler and disperse evenly. These ingredients give the coating antifouling and temperature-sensitive properties. The dispersion speed is 800-1500 rpm and the dispersion time is 10 minutes; then add the second component of composite antifouling agent, i.e. 30% of the mass of cuprous oxide antifouling agent and defoamer, disperse evenly and transfer to horizontal sand mill or basket sand mill for grinding to a fineness of less than 80 microns to obtain component A. The sand milling treatment is to further refine the particles of the coating and improve the uniformity and smoothness of the coating;

[0064] S2. Preparation of component B: Disperse the polyisocyanate and the second solvent uniformly according to the mass ratio to obtain component B. The dispersion speed is 800-1500 rpm and the dispersion time is 10-15 minutes. Stir thoroughly and evenly.

[0065] S3. Preparation of antifouling coating: Component A and component B are mixed uniformly in a mass ratio of 10:0.9-1.2 to obtain the temperature-controlled release and degradable antifouling coating, wherein the ratio of n(-NCO) / n(-OH) is 0.9-1.2:1.

[0066] In step S3, the polyisocyanate in component B reacts with the hydroxyl groups in component A during subsequent mixing, forming a crosslinked structure that enhances the coating's performance. Components A and B are mixed uniformly in a mass ratio of 10:0.9 to 1.2, ensuring a ratio of n(-NCO) (i.e., the isocyanate groups in the polyisocyanate) to n(-OH) (i.e., the hydroxyl groups in the polyol-degradable polyester copolymer) between 0.9 and 1.2:1. A n(-NCO) / n(-OH) ratio of 0.9 to 1.2:1 is crucial for ensuring sufficient crosslinking of the coating while preventing excess unreacted groups from remaining.

[0067] The present invention discloses a temperature-controlled release degradable antifouling coating and a preparation method thereof. The antifouling coating and the preparation method thereof are interrelated, and steps S1 to S3 of the preparation method are interrelated and inseparable. By precisely controlling the ratio and mixing order of the antifouling coating components, as well as the subsequent sanding and cross-linking reactions, the coating achieves multiple effects: first, it not only achieves a highly effective antifouling effect in sea areas with different temperatures; second, it possesses the degradation performance of the antifouling coating, does not rely on water flow to release the antifouling agent, and maintains an excellent antifouling effect even when moored; third, the raw materials for the preparation of the antifouling coating are abundant and inexpensive, and the synthesis process is simple, taking into account both product performance and cost control issues; fourth, the antifouling coating has excellent supporting properties and excellent antifouling performance, and a long antifouling life. A board coated with the antifouling coating remains free of blistering, cracking, and shedding after being immersed in shallow water for three years; fifth, it reduces the use of tie paint, thereby lowering production costs, while also greatly improving the adhesion of the antifouling coating.

[0068] Compared with the existing technology, the temperature-controlled release degradation antifouling coating provided by the present invention has the following technical principles and effects:

[0069] (1) The present invention has a temperature-controlled release degradable antifouling coating whose main body is a three-dimensional network structure formed by curing a polyhydroxy polymer and a polyisocyanate, so that the coating has excellent mechanical properties and adhesion properties, and can have excellent matching ability with the primer without the need for a connecting paint, thereby reducing material and construction costs.

[0070] (2) The antifouling coating of the present invention is prepared by compounding a degradable resin with a degradation function and a copolymer with a seawater temperature response function as a resin base material. The degradable resin can release the antifouling agent by breaking the ester bond under the action of seawater or biological enzymes. In a dynamic environment, the coating surface is naturally renewed to achieve a good antifouling effect. In a static environment, the released microenvironment has a high small molecule acid environment, which accelerates the degradation process of the coating and can break through the problem of poor static antifouling effect of traditional self-polishing antifouling coatings. The temperature-responsive functional copolymer, by introducing a thermosensitive monomer into the resin chain segment, utilizes its low-temperature hydrophilicity, the chain segment stretches to close the pores, and the high-temperature hydrophobicity, the chain segment shrinks to open the release channel, etc., to achieve the controlled release effect of the antifouling coating on the antifouling agent under different seawater temperature conditions, thereby improving the antifouling effect in high-temperature sea areas and the utilization efficiency of the antifouling agent in low-temperature sea areas.

[0071] (3) The antifouling coating of the present invention is prepared by adding a thermosensitive gel-coated antifouling agent, which can release more antifouling agent in high-temperature waters, further improving the antifouling performance of the coating in high-temperature waters.

[0072] (4) The introduction of fluorine-containing functional segments during the polymerization of the temperature-responsive copolymer used in the antifouling coating of the present invention improves the overall smoothness and surface condition of the coating, which has a positive effect on the antifouling effect of the coating.

[0073] The present invention is further illustrated by the following examples. The mass fractions of the raw materials of the temperature-controlled release degradation antifouling coatings of Examples 1 to 3 are shown in Table 1.

[0074] Table 1 Mass fractions of raw materials for temperature-controlled release of degradable antifouling coatings in Examples 1 to 3

[0075]

[0076]

[0077] Example 1

[0078] The present invention provides a temperature-controlled release and degradable antifouling coating, wherein the temperature-controlled release and degradable antifouling coating comprises:

[0079] Component A, comprising a polyhydroxy degradable polyester copolymer, a temperature-sensitive resin polymer, a composite antifouling agent, a temperature-sensitive gel-coated antifouling agent, an auxiliary antifouling agent, a defoaming agent, a pigment and filler, an anti-settling agent, and a first solvent;

[0080] Component B includes polyisocyanate and a second solvent.

[0081] The mass ratio of component A to component B is 10:0.9.

[0082] Specifically, the weight percentages of the raw materials of the temperature-controlled release degradation antifouling coating are shown in Table 1.

[0083] Specifically, the polyhydroxy degradable polyester copolymer is a copolymer prepared by polymerization of at least one monomer selected from valerolactone and lactic acid under the initiation of ethyl butyl propylene glycol, and has a molecular weight of 2000.

[0084] Specifically, the temperature-sensitive resin polymer is a polymer formed by free radical copolymerization of a temperature-sensitive monomer, a hydroxyl acrylic resin, and a fluorine-containing acrylic resin monomer under the action of an initiator. The molecular weight of the temperature-sensitive resin polymer is 6,000.

[0085] More specifically, the temperature-sensitive monomer is N-isopropylacrylamide.

[0086] More specifically, the hydroxy acrylic resin is hydroxy ethyl acrylate.

[0087] More specifically, the fluorine-containing acrylic resin monomer is trifluoroethyl methacrylate.

[0088] More specifically, the initiator is dibenzoyl peroxide.

[0089] More specifically, the preparation method of the temperature-sensitive resin polymer includes the following steps: adding 40 parts of a third solvent, 35 parts of a temperature-sensitive monomer, 4 parts of a hydroxyl acrylic resin, and 5 parts of a fluorine-containing acrylic resin into a reactor, heating the reactor to 80°C, dissolving 0.5 parts of an initiator in 10 parts of a third solvent, and adding the initiator dropwise to the reactor for 2 hours. After the initiator is added dropwise, the temperature is controlled to rise to 100°C and the reaction is continued for 6 hours, and then the material is cooled and discharged.

[0090] The third solvent is xylene and cyclohexanone.

[0091] Specifically, the first component of the composite antifouling agent is copper pyridinethione and 4,5-dichloro-2-n-octyl-3-isothiazolinone, and the second component is cuprous oxide.

[0092] The mass ratio of cuprous oxide, copper pyrithione and 4,5-dichloro-2-n-octyl-3-isothiazolinone is 40:5:5.

[0093] Specifically, the thermosensitive gel-coated antifouling agent is thermosensitive gel-coated bromopyrrole carbonitrile.

[0094] Specifically, the auxiliary antifouling agent is primary zinc oxide.

[0095] Specifically, the defoaming agent is defoaming agent 6600.

[0096] Specifically, the pigment and filler is talcum powder.

[0097] Specifically, the anti-settling agent is a slurry made of polyamide wax powder and xylene.

[0098] Specifically, the first solvent and the second solvent are xylene.

[0099] Specifically, the polyisocyanate is polyisocyanate N75.

[0100] In a second aspect of this embodiment, a method for preparing a temperature-controlled release degradable antifouling coating is provided. The method for preparing a temperature-controlled release degradable antifouling coating is used to prepare the above-mentioned temperature-controlled release degradable antifouling coating, and the preparation method comprises the following steps:

[0101] S1. Preparation of component A:

[0102] S11, adding the polyhydroxy degradable polyester copolymer, the temperature-sensitive resin polymer, 70% of the mass of the defoamer, the anti-settling agent and the first solvent into the drawing cylinder according to the mass ratio, mixing and dispersing at high speed to form a basic coating matrix;

[0103] S12, then add the first component of the composite antifouling agent, the temperature-sensitive gel-coated antifouling agent, the auxiliary antifouling agent and the pigment and filler and disperse them evenly. These ingredients give the coating antifouling and temperature-sensitive properties. The dispersion speed is 1500 rpm and the dispersion time is 10 minutes.

[0104] S13, then add the second component of the composite antifouling agent, namely 30% by weight of the cuprous oxide antifouling agent and the defoaming agent, and after uniform dispersion, transfer to a horizontal sand mill or a basket sand mill for grinding to a fineness of less than 80 microns to obtain component A. The sand milling process is to further refine the particles of the coating and improve the uniformity and smoothness of the coating;

[0105] S2. Preparation of component B: Disperse the polyisocyanate and the second solvent uniformly according to the mass ratio to obtain component B. The dispersion speed is 1500 rpm and the dispersion time is 10 minutes. Stir thoroughly.

[0106] S3. Preparation of antifouling coating: uniformly mixing component A and component B according to a mass ratio to obtain the temperature-controlled release and degradation antifouling coating.

[0107] Example 2

[0108] In this embodiment, different from that in embodiment 1, the weight percentages of the raw materials of the temperature-controlled release degradable antifouling coating are shown in Table 1.

[0109] The mass ratio of component A to component B is 10:1.

[0110] The polyhydroxy degradable polyester copolymer is a copolymer formed by polymerization of lactide and caprolactone monomers under the initiation of ethyl butyl propylene glycol. The molecular weight of the polyhydroxy degradable polyester copolymer is 3000.

[0111] Specifically, the molecular weight of the temperature-sensitive resin polymer is 10,000.

[0112] More specifically, the hydroxy acrylic resin is butyl hydroxy acrylate.

[0113] More specifically, the fluorine-containing acrylic resin monomer is hexafluorobutyl acrylate.

[0114] More specifically, the initiator is azobisisobutyronitrile.

[0115] More specifically, the preparation method of the temperature-sensitive resin polymer includes the following steps: adding 50 parts of a third solvent, 40 parts of a temperature-sensitive monomer, 5 parts of a hydroxylated acrylic resin, and 2 parts of a fluorinated acrylic resin into a reactor, heating the reactor to 90°C, dissolving 0.75 to 1 part of an initiator in 10 parts of the third solvent, and adding the initiator dropwise to the reactor for 2.5 hours. After the initiator is added dropwise, the temperature is controlled to rise to 90°C and the reaction is continued for 6 hours, and then the material is cooled and discharged.

[0116] The third solvent is xylene.

[0117] Specifically, the first component of the composite antifouling agent is copper pyrithione and bromopyrrole carbonitrile.

[0118] The mass ratio of cuprous oxide, copper pyrithione and bromopyrrole carbonitrile in the composite antifouling agent is 45:5:5.

[0119] Specifically, the thermosensitive gel-coated antifouling agent is thermosensitive gel-coated capsaicin.

[0120] Specifically, the defoaming agent is YRXP-06.

[0121] Specifically, the pigment filler is barite powder.

[0122] Specifically, the second solvent is xylene and ethyl acetate.

[0123] Specifically, the polyisocyanate is polyisocyanate N3390.

[0124] In the method for preparing a temperature-controlled release degradable antifouling coating described in this embodiment, in step S12, the dispersion speed is 1100 rpm.

[0125] In step S2, the dispersion speed is 1100 rpm and the dispersion time is 11 minutes.

[0126] Example 3

[0127] In this embodiment, different from that in embodiment 1, the weight percentages of the raw materials of the temperature-controlled release degradable antifouling coating are shown in Table 1.

[0128] The mass ratio of component A to component B is 10:1.2.

[0129] Specifically, the polyhydroxy degradable polyester copolymer is a copolymer prepared by polymerization of at least one monomer selected from caprolactone and glycolic acid under the initiation of ethyl butyl propylene glycol, and has a molecular weight of 4000.

[0130] Specifically, the temperature-sensitive resin polymer is a polymer formed by free radical copolymerization of a temperature-sensitive monomer, a hydroxyl acrylic resin, and a fluorine-containing acrylic resin monomer under the action of an initiator. The molecular weight of the temperature-sensitive resin polymer is 20,000.

[0131] More specifically, the fluorine-containing acrylic resin monomer is hexafluorobutyl acrylate.

[0132] More specifically, the preparation method of the temperature-sensitive resin polymer includes the following steps: adding 45 parts of a third solvent, 30 parts of a temperature-sensitive monomer, 2 parts of a hydroxylated acrylic resin, and 3 parts of a fluorinated acrylic resin into a reactor, heating the reactor to 85°C, dissolving 1 part of an initiator in 10 parts of a third solvent, and adding the mixture dropwise to the reactor for 3 hours. After the initiator is added dropwise, the temperature is controlled to rise to 95°C and the reaction is continued for 6 hours, and then the material is cooled and discharged.

[0133] The third solvent is cyclohexanone.

[0134] Specifically, the first component of the composite antifouling agent is zinc pyrithione, medetomidine and 4,5-dichloro-2-n-octyl-3-isothiazolinone.

[0135] The mass ratio of cuprous oxide, copper pyrithione and 4,5-dichloro-2-n-octyl-3-isothiazolinone is 45:5:5.

[0136] Specifically, the thermosensitive gel-coated antifouling agent is a thermosensitive gel-coated diterpene formamide compound.

[0137] Specifically, the polyisocyanate is polyisocyanate L75.

[0138] Specifically, the defoaming agents are defoaming agent 6600 and YRXP-06.

[0139] Specifically, the pigments and fillers are talc powder and barite powder.

[0140] In the method for preparing a temperature-controlled release degradable antifouling coating described in this embodiment, in step S12, the dispersion speed is 800 rpm.

[0141] In step S2, the dispersion speed is 800 rpm and the dispersion time is 15 minutes.

[0142] Comparative Example 1

[0143] The antifouling coating was prepared using the coating components and preparation method of Example 1 of the patent application number CN201911104831.2.

[0144] Performance Testing

[0145] 1. Copper ion leakage rate

[0146] The antifouling coating prepared in Example 2 was applied to a panel. The primer in the matching coating was H44-61 epoxy antirust primer, and no tie coat was required. The copper ion permeation rate of the antifouling coating prepared in the present invention was tested under different temperature conditions. The copper ion permeation rate test was carried out in accordance with the standard GB / T 6824-2008 "Determination of copper ion permeation rate of ship bottom antifouling paint". The copper ion permeation rate of the antifouling coating was tested in artificial seawater at 15°C and 30°C respectively. The test data are shown in FIG. Figure 1 shown.

[0147] from Figure 1 It can be found that the copper ion leakage rate of the antifouling coating tested at 30°C is significantly greater than that at 15°C, indicating that the invented antifouling coating has temperature-sensitive properties and can adjust the antifouling agent leakage rate according to temperature changes.

[0148] 2. Shallow sea hanging board test and adhesion test

[0149] The antifouling coating prepared in Example 2 was applied to the prepared board, and the primer in the matching coating layer was H44-61 epoxy antirust primer, without the need for a tie paint; the antifouling coating prepared in Comparative Example 1 was applied to the prepared board, and the primer in the matching coating layer was H44-61 epoxy antirust primer, and a tie paint was used, which was a tie paint commonly used in the prior art.

[0150] The panels coated with the antifouling coatings of Example 2 and Comparative Example 1 were subjected to real sea trials in the waters of Sanya and Xiamen, respectively. The tests were conducted in accordance with GB / T 5370-2007, "Test Method for Shallow Sea Immersion of Antifouling Paint Samples." The panels were immersed in the sea for three years, and the performance of the panels after one and three years in the shallow sea was observed and statistically analyzed. The results are shown in Table 2. Figure 2 and Figure 3 ,in, Figure 2 It is in the waters of Sanya. Figure 3 This is the water temperature in Xiamen waters. The water temperature in Sanya waters is higher than that in Xiamen waters.

[0151] Adhesion tests were conducted on the panels coated with the antifouling coatings of Example 2 and Comparative Example 1, with reference to GB / T5210-2006 "Paint and varnish adhesion test by pull-off method". The results are shown in Table 2.

[0152] Table 2 Antifouling performance results of Examples 1 to 3 and Comparative Example 1 tested with a shallow sea scraper

[0153]

[0154] Figure 2 This is a schematic diagram of the test results of a temperature-controlled release degradation antifouling coating according to Example 2 of the present invention applied on a panel and immersed in the shallow waters of Sanya for three years; Figure 3This is a schematic diagram of the test results of a temperature-controlled release degradation antifouling coating according to Example 2 of the present invention applied on a panel and immersed in the shallow waters of Xiamen for three years.

[0155] from Figure 2 and Figure 3 It can be found that after the panels coated with the antifouling coating prepared in Example 2 were immersed in shallow sea water for three years in two sea areas, no fouling organisms were attached to the surface of the temperature-controlled release degradation antifouling coating, the paint film was intact, and there was no blistering, cracking, or shedding. The antifouling coating showed no fouling phenomenon, and the comprehensive antifouling score was 100 points, indicating that the antifouling coating of the present invention has excellent supporting performance and excellent antifouling performance, and a long antifouling time.

[0156] Figure 4 This is a schematic diagram of adhesion test results of an antifouling coating capable of temperature-controlled release of degradation as described in Example 2 of the present invention, applied on a prepared board.

[0157] from Figure 4 It can be found that the applicant tested five test points respectively, and the adhesion of the five test points were 3.57MPa, 4.30MPa, 4.33MPa, 4.10MPa and 4.23MPa respectively; the average adhesion was 4.11MPa.

[0158] From Table 2 we can find that:

[0159] (1) Compared with the panels coated with the antifouling coating prepared in Comparative Example 1, the panels coated with the antifouling coating prepared in Example 2 not only reduced the use of tie paint and reduced production costs, but also greatly improved the adhesion of the antifouling coating. The average adhesion of the panels coated with the antifouling coating prepared in Example 2 was 2.7 times that of the panels coated with the antifouling coating prepared in Comparative Example 1.

[0160] (2) After being immersed in the shallow sea of ​​two sea areas for one year, the plates coated with the antifouling coating prepared in Comparative Example 1 had no fouling organisms attached to the surface of the antifouling coating, and the paint film was intact without blistering, cracking, or shedding. However, after being immersed for three years, the antifouling coating showed slight blistering, no cracking, and no shedding, and the antifouling coating showed fouling. The comprehensive antifouling score in the Sanya sea area was 86 points, and the comprehensive antifouling score in the Xiamen sea area was 88 points.

[0161] (3) After being immersed in the shallow sea of ​​two sea areas for 1 year or 3 years, the panels coated with the antifouling coating prepared in Example 2 showed no fouling organisms attached to the surface of the temperature-controlled release degradation antifouling coating, and the paint film was intact without blistering, cracking, or shedding. The comprehensive antifouling score was 100 points, indicating that the antifouling coating of the present invention has excellent supporting performance and antifouling performance, and the antifouling time is very long.

[0162] Although the present invention is disclosed as above, the present invention is not limited thereto. Any person skilled in the art can make various changes and modifications without departing from the spirit and scope of the present invention. Therefore, the scope of protection of the present invention should be based on the scope defined by the claims.

Claims

1. A temperature-controlled release degradable antifouling coating, characterized in that: The antifouling coating comprises: Component A, comprising a polyhydroxy degradable polyester copolymer, a temperature-sensitive resin polymer, a composite antifouling agent, a temperature-sensitive gel-coated antifouling agent, an auxiliary antifouling agent, a defoaming agent, a pigment and filler, an anti-settling agent, and a first solvent; Component B, comprising a polyisocyanate and a second solvent; The mass ratio of component A to component B is 10:0.9-1.2; The temperature-sensitive resin polymer is a polymer formed by free radical copolymerization of a temperature-sensitive monomer, a hydroxylated acrylic resin, and a fluorinated acrylic resin monomer under the action of an initiator; the temperature-sensitive monomer is N-isopropylacrylamide; the hydroxylated acrylic resin is at least one of hydroxylated ethyl acrylate and hydroxylated butyl acrylate; and the fluorinated acrylic resin monomer is at least one of trifluoroethyl methacrylate and hexafluorobutyl acrylate.

2. The temperature-controlled release degradable antifouling coating according to claim 1, characterized in that: The component A comprises the following components in parts by mass: 15-25 parts of a polyhydroxy degradable polyester copolymer, 3-10 parts of a temperature-sensitive resin polymer, 50-60 parts of a composite antifouling agent, 1-3 parts of a temperature-sensitive gel-coated antifouling agent, 4-10 parts of an auxiliary antifouling agent, 0.5-1 parts of a defoaming agent, 1-5 parts of a pigment and filler, 0.5-1 parts of an anti-settling agent, and 4-6 parts of a first solvent; The component B includes the following components in parts by mass: 2.5 to 4 parts of polyisocyanate and 6.5 to 8 parts of a second solvent.

3. The temperature-controlled release degradable antifouling coating according to claim 2, characterized in that: The polyhydroxy degradable polyester copolymer is a copolymer prepared by polymerization of at least one monomer selected from lactide, valerolactone, caprolactone, lactic acid and glycolic acid under the initiation of ethyl butyl propylene glycol.

4. The temperature-controlled release degradable antifouling coating according to claim 1, characterized in that: The composite antifouling agent comprises a first component and a second component, wherein the first component is at least one of bromopyrrolecarbonitrile, copper pyrithione, zinc pyrithione, medetomidine and 4,5-dichloro-2-n-octyl-3-isothiazolinone, and the second component is cuprous oxide.

5. The temperature-controlled release degradable antifouling coating according to claim 1, characterized in that: The temperature-sensitive gel-coated antifouling agent is a temperature-sensitive gel-coated at least one of bromopyrrole carbonitrile, capsaicin and diterpene carboxamide compounds.

6. The temperature-controlled release degradable antifouling coating according to claim 1, characterized in that: The auxiliary antifouling agent is primary zinc oxide.

7. The temperature-controlled release degradable antifouling coating according to claim 1, characterized in that: The polyisocyanate is at least one of polyisocyanate N3390, polyisocyanate N75 or polyisocyanate L75.

8. The temperature-controlled release degradable antifouling coating according to claim 1, characterized in that: The first solvent and the second solvent are at least one of xylene and ethyl acetate.

9. A method for preparing a temperature-controlled release degradable antifouling coating, characterized in that: The method for preparing a temperature-controlled release degradable antifouling coating is used to prepare the temperature-controlled release degradable antifouling coating according to any one of claims 1 to 8, and the method comprises the following steps: S1. Preparation of component A: Disperse the polyhydroxy degradable polyester copolymer, the thermosensitive resin polymer, 70% of the mass of the defoamer, the anti-settling agent, and the first solvent at high speed in a mass ratio, then add the first component of the composite antifouling agent, the thermosensitive gel-coated antifouling agent, the auxiliary antifouling agent, and the pigment and filler, and disperse them evenly; then add the second component of the composite antifouling agent and 30% of the mass of the defoamer, disperse them evenly, and then sand grind to obtain component A; S2. Preparation of component B: uniformly disperse the polyisocyanate and the second solvent according to the mass ratio to obtain component B; S3. Preparation of antifouling coating: uniformly mixing component A and component B at a mass ratio of 10:0.9-1.2 to obtain the temperature-controlled release and degradation antifouling coating.

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