Antifouling and anticorrosive paint based on bio-based material and preparation method of antifouling and anticorrosive paint

Abstract

The invention provides a bio-based material-based antifouling anticorrosive paint, which comprises a primer and a finish, the primer comprises a component A and a component B, and the finish comprises a component A and a component C; the component A is prepared from the following components in parts by weight: 25 to 35 parts of first bio-based polyol, 20 to 30 parts of polymethylene polyphenyl polyisocyanate, 0.1 to 0.5 part of triphenyl phosphite, 15 to 30 parts of environment-friendly solvent and 5 to 8 parts of low surface energy modifier; the component B is prepared from 30 to 40 parts of second bio-based polyol and 100 to 130 parts of first pigment; the component C is prepared from 30 to 40 parts of third bio-based polyol, 15 to 20 parts of second pigment, 15 to 22 parts of coupling agent, 5 to 10 parts of environment-friendly antifouling agent, 3 to 6 parts of structural aid and 80 to 100 parts of anticorrosive pigment. Related preparation methods are also provided. The coating provided by the invention can realize efficient cooperation of antifouling and anticorrosion functions, is green and environment-friendly in the whole life cycle, and is durable in a dynamic service environment.

Description

Technical Field

[0001] This invention relates to the field of industrial protective coatings, and more specifically, to the field of antifouling and anticorrosion coatings, particularly to an antifouling and anticorrosion coating based on bio-based materials and its preparation method. Background Technology

[0002] Industrial protective coatings are coatings used for surface protection of industrial production equipment, steel structures, ships, bridges, etc. They are mainly used in machinery, chemical, shipbuilding, power and other fields. Their base materials include asphalt, alkyd, epoxy, polyurethane and fluorocarbon resins, etc. According to function, they can be divided into special paints such as waterproof and fireproof paints. The construction methods include spraying, brushing and roller coating.

[0003] In marine engineering, shipbuilding, chemical storage tanks, and cross-sea infrastructure, substrates are constantly subjected to corrosive media such as seawater and salt spray, and are also susceptible to adhesion by marine organisms such as barnacles and algae. This damage significantly reduces the service life of the substrates and generates substantial maintenance costs. Therefore, high-performance antifouling and anticorrosion coatings have become an indispensable part of marine engineering.

[0004] Current mainstream industry solutions fall into two categories: "layered coating" and "integrated coating." Layered coating requires applying an anti-corrosion primer and an anti-fouling topcoat sequentially. This approach has significant drawbacks. The adhesion between the primer and topcoat is easily affected by the application process and compatibility, leading to interlayer peeling after long-term service, causing the dual protective functions to fail simultaneously. Furthermore, the two coating processes extend the construction cycle, and the anti-fouling components in the topcoat may penetrate into the primer, weakening the corrosion inhibition effect and making it difficult to achieve functional synergy.

[0005] Integrated coatings present several problems. Most products combine anti-corrosion materials and antifouling agents through physical mixing to achieve synergistic effects. However, these two materials have poor compatibility, easily leading to uneven concentrations in certain areas. This can cause coating cracking or weakened protective effects, failing to meet the long-term protection requirements of marine engineering. Regarding antifouling agents, traditional organotin-based antifouling agents are banned by the International Maritime Organization due to their strong biotoxicity. Fluorine-containing low-surface-energy agents are not only highly environmentally cumulative but also expensive, presenting significant drawbacks. Some products use high-VOC solvents such as xylene, resulting in excessive emissions that do not comply with relevant environmental regulations. The durability of integrated coating products is relatively weak. In environmentally friendly products, antifouling agents are mostly dispersed through physical adsorption, failing to form a chemical bond with the substrate. This makes them prone to rapid dissolution under seawater erosion, resulting in a short antifouling lifespan.

[0006] Therefore, there is a need for an antifouling and anticorrosion coating that can achieve efficient synergy between antifouling and anticorrosion functions, be environmentally friendly throughout its entire life cycle, and be durable in dynamic service environments. This would address the core shortcomings of existing antifouling and anticorrosion coatings and meet the urgent needs of marine engineering and other fields for high-performance, low-pollution, and long-life protective materials. Summary of the Invention

[0007] In order to overcome the shortcomings of the prior art, one objective of the present invention is to provide a bio-based antifouling and anticorrosion coating that can achieve efficient synergy of antifouling and anticorrosion functions, green and environmentally friendly throughout the entire life cycle, and durable in dynamic service environments. This addresses the core shortcomings of existing antifouling and anticorrosion coatings, meets the urgent needs of marine engineering and other fields for high-performance, low-pollution, and long-life protective materials, and is suitable for large-scale promotion and application.

[0008] Another objective of this invention is to provide a method for preparing antifouling and anticorrosive coatings based on bio-based materials. The preparation process is simple, easy to operate, and has low cost, making it suitable for large-scale application.

[0009] To achieve the above objectives, in a first aspect of the present invention, a bio-based antifouling and anticorrosive coating is provided, comprising a primer and a topcoat, characterized in that the primer comprises component A and component B, and the topcoat comprises component A and component C;

[0010] The first component comprises 25 to 35 parts by weight of a first bio-based polyol, 20 to 30 parts by weight of polymethylene polyphenyl polyisocyanate, 0.1 to 0.5 parts by weight of triphenyl phosphite, 15 to 30 parts by weight of an environmentally friendly solvent, and 5 to 8 parts by weight of a low surface energy modifier.

[0011] The B component comprises 30 to 40 parts by weight of the second bio-based polyol and 100 to 130 parts by weight of the first pigment;

[0012] The C component comprises 30 to 40 parts by weight of a third bio-based polyol, 15 to 20 parts by weight of a second pigment, 15 to 22 parts by weight of a coupling agent, 5 to 10 parts by weight of an environmentally friendly antifouling agent, 3 to 6 parts by weight of a structural aid, and 80 to 100 parts by weight of an anticorrosive pigment.

[0013] Preferably, the first bio-based polyol, the second bio-based polyol, and the third bio-based polyol are all castor oil, the castor oil having an acid value of 0.1 mg KOH / g to 0.2 mg KOH / g and a hydroxyl value of 160 mg KOH / g to 185 mg KOH / g.

[0014] Preferably, the environmentally friendly solvent is one of turpentine and dimethyl carbonate; the low surface energy modifier is monohydroxy polydimethylsiloxane; the first pigment and the second pigment are both one of iron oxide red and titanium dioxide; the coupling agent is 3-(2,3-epoxypropoxy)propyltrimethoxysilane; the environmentally friendly antifouling agent is one of nano zinc oxide and chitosan-modified graphene oxide; the structural aid is nano silica; or, the anticorrosive pigment is one of zinc phosphate and mica iron oxide.

[0015] Preferably, in the primer, the amount of component B added is 15% of the weight of component A; or, in the topcoat, the mass ratio of component A to component C is 1:2.

[0016] In a second aspect of the present invention, a method for preparing the above-mentioned antifouling and anticorrosive coating based on bio-based materials is provided, characterized by comprising the following steps:

[0017] (1) Preparation of the A component

[0018] (11) The first bio-based polyol and the triphenyl phosphite are subjected to dehydration treatment to obtain a dehydrated product;

[0019] (12) The low surface energy modifier is added to the dehydrated product and stirred to obtain the stirred product;

[0020] (13) Add the polymethylene polyphenyl polyisocyanate and the environmentally friendly solvent to the stirred product, mix thoroughly and evenly, then heat and stir, then heat and keep warm to carry out the polymerization reaction, and obtain the A component;

[0021] (2) Preparation of the B component

[0022] (21) Stir and mix the second bio-based polyol and the first pigment to obtain a premix;

[0023] (22) The premix is ​​subjected to fine grinding and dispersion treatment to obtain component B;

[0024] (3) Preparation of the C component

[0025] (31) Stir and mix the third bio-based polyol, the coupling agent and the structural aid to obtain a pre-dispersion;

[0026] (32) Add the second pigment, the environmentally friendly antifouling agent and the anticorrosive pigment to the pre-dispersed material and stir evenly to obtain a premixed material;

[0027] (33) The premixed material is finely ground and dispersed to obtain component C;

[0028] (4) Preparation of the primer

[0029] Add component B to component A and stir until homogeneous;

[0030] (5) Preparation of the topcoat

[0031] Add component C to component A and stir until homogeneous.

[0032] Preferably, in step (11), the vacuum degree of the dehydration treatment is not less than 0.096 MPa, the temperature of the dehydration treatment is controlled within the range of 105°C to 120°C, and the dehydration treatment lasts for more than 1.5 hours; in step (12), the stirring speed is 1000 to 1100 revolutions per minute, and the stirring time is 30 minutes; or, in step (13), the heating and stirring speed is 1000 to 1100 revolutions per minute, the heating and stirring temperature is 40°C to 45°C, the heating and stirring time is half an hour, the heating rate is 3°C per minute, the holding temperature is 70°C to 75°C, and the holding time is 1.5 to 2 hours.

[0033] Preferably, in step (21), the stirring speed is 1000 to 1100 revolutions per minute, and the stirring time is 30 minutes; or, in step (22), the fine grinding and dispersion process is 40 revolutions per minute, and the fine grinding and dispersion process is 2 to 3 hours.

[0034] Preferably, in step (31), the stirring speed is 1000 to 1100 revolutions per minute, and the stirring time is 30 minutes; in step (32), the stirring speed is 1000 to 1100 revolutions per minute, and the stirring time is 60 minutes; or, in step (33), the fine grinding and dispersion treatment speed is 40 revolutions per minute, and the fine grinding and dispersion treatment time is 3 to 4 hours.

[0035] Preferably, in step (41), the amount of component B added is 15% of the weight of component A; or, in step (51), the mass ratio of component A to component C is 1:2.

[0036] In a third aspect of the present invention, a bio-based antifouling and anticorrosive coating is provided, characterized in that it is prepared by the above-described method for preparing a bio-based antifouling and anticorrosive coating.

[0037] The beneficial effects of this invention are as follows:

[0038] 1. The antifouling and anticorrosive coating based on bio-based materials of the present invention includes a primer and a topcoat. The primer includes component A and component B, and the topcoat includes component A and component C. Component A includes 25 to 35 parts by weight of a first bio-based polyol, 20 to 30 parts by weight of polymethylene polyphenyl polyisocyanate, 0.1 to 0.5 parts by weight of triphenyl phosphite, 15 to 30 parts by weight of an environmentally friendly solvent, and 5 to 8 parts by weight of a low surface energy modifier; component B includes 30 to 40 parts by weight of a second bio-based polyol and 100 to 130 parts by weight of a first pigment; component C... It comprises 30-40 parts by weight of a third bio-based polyol, 15-20 parts by weight of a second pigment, 15-22 parts by weight of a coupling agent, 5-10 parts by weight of an environmentally friendly antifouling agent, 3-6 parts by weight of a structural additive, and 80-100 parts by weight of an anticorrosive pigment. Therefore, it can achieve efficient synergy between antifouling and anticorrosive functions, green and environmentally friendly throughout its entire life cycle, and durable in dynamic service environments. This addresses the core shortcomings of existing antifouling and anticorrosive coatings, meets the urgent needs of marine engineering and other fields for high-performance, low-pollution, and long-life protective materials, and is suitable for large-scale promotion and application.

[0039] 2. The preparation method of the above-mentioned antifouling and anticorrosive coating based on bio-based materials of the present invention includes the following steps: (1) Preparation of component A: the first bio-based polyol and triphenyl phosphite are dehydrated to obtain a dehydrated product; a low surface energy modifier is added to the dehydrated product and stirred to obtain a stirred product; polymethylene polyphenyl polyisocyanate and environmentally friendly solvent are added to the stirred product, mixed thoroughly and evenly, then heated and stirred, and then heated and kept warm to carry out the polymerization reaction; (2) Preparation of component B: the second bio-based polyol and the first pigment are stirred and mixed to obtain a premix; the premix is ​​then mixed with the first pigment and stirred ... (3) Preparation of component C: Mix the third bio-based polyol, coupling agent and structural aid to obtain a pre-dispersed material; add the second pigment, environmentally friendly antifouling agent and anticorrosive pigment to the pre-dispersed material and stir evenly to obtain a premixed material; perform fine grinding and dispersion treatment on the premixed material; (4) Preparation of primer: add component B to component A and stir evenly; (5) Preparation of topcoat: add component C to component A and stir evenly. Therefore, its preparation process is simple, easy to prepare, easy to operate, and has low preparation cost, making it suitable for large-scale promotion and application.

[0040] These and other objects, features and advantages of the present invention will be fully apparent from the following detailed description and drawings, and can be achieved by the methods, means and combinations thereof specifically pointed out in the specification. Attached Figure Description

[0041] Figure 1 This is a schematic diagram of the process flow for preparing the antifouling and anticorrosion coating based on bio-based materials according to the present invention. Detailed Implementation

[0042] To meet the urgent need for high-performance, low-pollution, and long-life protective coatings in fields such as marine engineering, and to adapt to existing production processes and reduce costs, the inventors conducted extensive research and proposed an antifouling and anticorrosion coating based on bio-based materials. The system is constructed with bio-based materials to achieve synergistic antifouling and anticorrosion functions, taking into account both green environmental protection and durability, meeting the long-term protection needs of fields such as marine engineering, and adapting to existing production processes to reduce costs. Based on this, the present invention was completed.

[0043] This invention first provides a bio-based antifouling and anticorrosive coating, comprising a primer and a topcoat, wherein the primer comprises component A and component B, and the topcoat comprises component A and component C;

[0044] The first component comprises 25 to 35 parts by weight of a first bio-based polyol, 20 to 30 parts by weight of polymethylene polyphenyl polyisocyanate, 0.1 to 0.5 parts by weight of triphenyl phosphite, 15 to 30 parts by weight of an environmentally friendly solvent, and 5 to 8 parts by weight of a low surface energy modifier.

[0045] The B component comprises 30 to 40 parts by weight of the second bio-based polyol and 100 to 130 parts by weight of the first pigment;

[0046] The C component comprises 30 to 40 parts by weight of a third bio-based polyol, 15 to 20 parts by weight of a second pigment, 15 to 22 parts by weight of a coupling agent, 5 to 10 parts by weight of an environmentally friendly antifouling agent, 3 to 6 parts by weight of a structural aid, and 80 to 100 parts by weight of an anticorrosive pigment.

[0047] The first bio-based polyol, the second bio-based polyol, and the third bio-based polyol can be any suitable bio-based polyol. Preferably, the first bio-based polyol, the second bio-based polyol, and the third bio-based polyol are all castor oil, the castor oil having an acid value of 0.1 mg KOH / g to 0.2 mg KOH / g and a hydroxyl value of 160 mg KOH / g to 185 mg KOH / g.

[0048] The environmentally friendly solvent can be any suitable environmentally friendly solvent, preferably, it is one of turpentine and dimethyl carbonate.

[0049] The low surface energy modifier can be any suitable low surface energy modifier, preferably a monohydroxy polydimethylsiloxane.

[0050] The first pigment and the second pigment can be any suitable pigment, preferably, the first pigment and the second pigment are both iron oxide red and titanium dioxide.

[0051] The coupling agent can be any suitable coupling agent, preferably 3-(2,3-epoxypropoxy)propyltrimethoxysilane.

[0052] The environmentally friendly antifouling agent can be any suitable environmentally friendly antifouling agent, preferably, it is one of nano zinc oxide and chitosan-modified graphene oxide.

[0053] The structural aid can be any suitable structural aid, preferably nano-silica.

[0054] The anti-corrosion pigment can be any suitable anti-corrosion pigment, preferably, it is one of zinc phosphate and mica iron oxide.

[0055] In the primer, the amount of component B added can be determined as needed. Preferably, in the primer, the amount of component B added is 15% of the weight of component A.

[0056] In the topcoat, the mass ratio of component A to component C can be determined as needed. Preferably, in the topcoat, the mass ratio of component A to component C is 1:2.

[0057] This invention also provides a method for preparing the above-mentioned antifouling and anticorrosive coating based on bio-based materials (see...). Figure 1 (As shown), including the following steps:

[0058] (1) Preparation of the A component

[0059] (11) The first bio-based polyol and the triphenyl phosphite are subjected to dehydration treatment to obtain a dehydrated product;

[0060] (12) The low surface energy modifier is added to the dehydrated product and stirred to obtain the stirred product;

[0061] (13) Add the polymethylene polyphenyl polyisocyanate and the environmentally friendly solvent to the stirred product, mix thoroughly and evenly, then heat and stir, then heat and keep warm to carry out the polymerization reaction, and obtain the A component;

[0062] (2) Preparation of the B component

[0063] (21) Stir and mix the second bio-based polyol and the first pigment to obtain a premix;

[0064] (22) The premix is ​​subjected to fine grinding and dispersion treatment to obtain component B;

[0065] (3) Preparation of the C component

[0066] (31) Stir and mix the third bio-based polyol, the coupling agent and the structural aid to obtain a pre-dispersion;

[0067] (32) Add the second pigment, the environmentally friendly antifouling agent and the anticorrosive pigment to the pre-dispersed material and stir evenly to obtain a premixed material;

[0068] (33) The premixed material is finely ground and dispersed to obtain component C;

[0069] (4) Preparation of the primer

[0070] Add component B to component A and stir until homogeneous;

[0071] (5) Preparation of the topcoat

[0072] Add component C to component A and stir until homogeneous.

[0073] In step (11), the vacuum degree, temperature and time of the dehydration treatment can be determined as needed. Preferably, in step (11), the vacuum degree of the dehydration treatment is not less than 0.096 MPa, the temperature of the dehydration treatment is controlled within the range of 105°C to 120°C, and the time of the dehydration treatment lasts for more than 1.5 hours.

[0074] In step (12), the stirring speed and time can be determined as needed. Preferably, in step (12), the stirring speed is 1000 to 1100 revolutions per minute and the stirring time is 30 minutes.

[0075] In step (13), the heating and stirring speed, temperature and time, the heating rate, and the holding temperature and time can be determined as needed. Preferably, in step (13), the heating and stirring speed is 1000 to 1100 revolutions per minute, the heating and stirring temperature is 40°C to 45°C, the heating and stirring time is half an hour, the heating rate is 3°C per minute, the holding temperature is 70°C to 75°C, and the holding time is 1.5 to 2 hours.

[0076] In step (21), the stirring speed and time can be determined as needed. Preferably, in step (21), the stirring speed is 1000 to 1100 revolutions per minute and the stirring time is 30 minutes.

[0077] In step (22), the speed and time of the fine grinding and dispersion treatment can be determined as needed. Preferably, in step (22), the speed of the fine grinding and dispersion treatment is 40 revolutions per minute, and the time of the fine grinding and dispersion treatment is 2 to 3 hours.

[0078] In step (31), the stirring speed and time can be determined as needed. Preferably, in step (31), the stirring speed is 1000 to 1100 revolutions per minute and the stirring time is 30 minutes.

[0079] In step (32), the speed and time of stirring can be determined as needed. Preferably, in step (32), the speed of stirring is 1000 to 1100 revolutions per minute, and the time of stirring is 60 minutes.

[0080] In step (33), the speed and time of the fine grinding and dispersion treatment can be determined as needed. Preferably, in step (33), the speed of the fine grinding and dispersion treatment is 40 revolutions per minute, and the time of the fine grinding and dispersion treatment is 3 to 4 hours.

[0081] In step (41), the amount of component B added can be determined as needed. Preferably, in step (41), the amount of component B added is 15% of the weight of component A.

[0082] In step (51), the mass ratio of component A to component C can be determined as needed. Preferably, in step (51), the mass ratio of component A to component C is 1:2.

[0083] The present invention also provides a bio-based antifouling and anticorrosive coating, which is prepared by the above-described preparation method of the bio-based antifouling and anticorrosive coating.

[0084] To provide a clearer understanding of the technical content of this invention, the following embodiments are provided for detailed description. It should be understood that the specific embodiments described herein are merely illustrative and not intended to limit the invention. Unless otherwise specified, the raw materials used in the following embodiments are all available through conventional commercial channels.

[0085] Example 1

[0086] Bio-based antifouling and anticorrosive coatings include a primer and a topcoat. The primer includes component A and component B; the topcoat includes component A and component C.

[0087] Component A, by weight: 25 parts castor oil, 20 parts polymethylene polyphenyl polyisocyanate, 0.1 parts triphenyl phosphite, 15 parts turpentine oil, and 5 parts monohydroxy polydimethylsiloxane (PDMS-OH).

[0088] Component B, by weight: 30 parts castor oil, 100 parts titanium dioxide.

[0089] Component C, by weight: 30 parts castor oil, 15 parts titanium dioxide, 15 parts 3-(2,3-epoxypropoxy)propyltrimethoxysilane, 5 parts nano zinc oxide, 3 parts nano silica, and 80 parts zinc phosphate.

[0090] Castor oil (Jinan Huamao Chemical Co., Ltd., refined castor oil), acid value 0.1 mg KOH / g, hydroxyl value 160 mg KOH / g.

[0091] The preparation process of component A is as follows: Triphenyl phosphite and castor oil are added to a reaction vessel and dehydrated at 105°C under a vacuum of 0.096 MPa for 1.5 hours. After dehydration, monohydroxy polydimethylsiloxane (PDMS-OH) is added to the vessel and stirred at 1000 rpm for 30 minutes. Then, polymethylene polyphenyl polyisocyanate and turpentine are added and thoroughly mixed. The temperature is adjusted to 40°C, and the stirring speed is maintained at 1000 rpm for half an hour. The temperature is then increased to 70°C at a rate of 3°C per minute and maintained at 70°C for 2 hours to carry out the polymerization reaction. After the reaction, the product is cooled to below 45°C, filtered through a wire mesh, and then sealed for storage.

[0092] The preparation process for component B is as follows: castor oil and titanium dioxide are placed in a mixing container and stirred at 1000 revolutions per minute for 30 minutes to form a premix. The premix is ​​then transferred to a three-roll mill for fine grinding and dispersion at 40 revolutions per minute for 2 hours to ensure sufficient shearing and dispersion, resulting in a uniform and fine paste. The final ground product has a fineness of 17 μm.

[0093] The preparation process of component C is as follows: castor oil, 3-(2,3-epoxypropoxy)propyltrimethoxysilane, and nano-silica are placed in a mixing container and stirred at 1000 rpm for 30 minutes to form a pre-dispersed material; then titanium dioxide, nano-zinc oxide, and zinc phosphate are added to the container and stirred at 1000 rpm for 60 minutes to form a uniform premix; finally, the premix is ​​transferred to a three-roll mill for fine grinding and dispersion at 40 rpm for 3 hours to ensure that the material undergoes sufficient shearing and dispersion to form a uniform and fine paste with a fineness of 17 μm.

[0094] The primer for the antifouling and anticorrosion coating is made by adding component B to component A at 15% of the mass of component A and stirring until homogeneous before application.

[0095] The topcoat of the antifouling and anticorrosive coating is prepared by mixing component A and component C in a dry container at a mass ratio of 1:2, and then applying it to the surface.

[0096] Example 2

[0097] Bio-based antifouling and anticorrosive coatings include a primer and a topcoat. The primer includes component A and component B; the topcoat includes component A and component C.

[0098] Component A, by weight: 28 parts castor oil, 23 parts polymethylene polyphenyl polyisocyanate, 0.2 parts triphenyl phosphite, 20 parts dimethyl carbonate, and 6 parts monohydroxy polydimethylsiloxane (PDMS-OH).

[0099] Component B, by weight: 33 parts castor oil, 110 parts iron oxide red.

[0100] Component C, by weight: 33 parts castor oil, 17 parts iron oxide red, 17 parts 3-(2,3-epoxypropoxy)propyltrimethoxysilane, 7 parts chitosan-modified graphene oxide (Xi'an Qiyue Biotechnology Co., Ltd., purity 98%), 4 parts nano silica, and 85 parts mica iron oxide.

[0101] Castor oil (Jinan Huamao Chemical Co., Ltd., refined castor oil), acid value 0.15mgKOH / g, hydroxyl value 170mgKOH / g.

[0102] The preparation process of component A is as follows: Triphenyl phosphite and castor oil are added to a reaction vessel and dehydrated at 110°C under a vacuum of 0.096 MPa for 2 hours. After dehydration, monohydroxy polydimethylsiloxane (PDMS-OH) is added to the vessel and stirred at 1100 rpm for 30 minutes. Then, polymethylene polyphenyl polyisocyanate and dimethyl carbonate are added and thoroughly mixed. The temperature is adjusted to 42°C, and the stirring speed is 1100 rpm for half an hour. The temperature is then increased to 75°C at a rate of 3°C per minute and maintained at 75°C for 1.5 hours for polymerization. After the reaction, the product is cooled to below 45°C, filtered through a wire mesh, and then sealed for storage.

[0103] The preparation process of component B is as follows: castor oil and iron oxide red are placed in a mixing container and stirred at 1100 rpm for 30 minutes to prepare a premix. The premix is ​​then transferred to a three-roll mill for fine grinding and dispersion at 40 rpm for 2.5 hours to ensure sufficient shearing and dispersion, resulting in a uniform and fine paste. The final ground product has a fineness of 16 μm.

[0104] The preparation process of component C is as follows: castor oil, 3-(2,3-epoxypropoxy)propyltrimethoxysilane, and nano-silica are placed in a mixing container and stirred at 1100 rpm for 30 minutes to form a pre-dispersed material; then iron oxide red, chitosan-modified graphene oxide, and mica iron oxide are added to the container and stirred at 1100 rpm for 60 minutes to form a uniform premix; finally, the premix is ​​transferred to a three-roll mill for fine grinding and dispersion at 40 rpm for 3.5 hours to ensure that the material undergoes sufficient shearing and dispersion to form a uniform and fine paste with a fineness of 16 μm.

[0105] The primer for the antifouling and anticorrosive coating is made by adding component B to component A at 15% of the mass of component A and stirring until homogeneous before application.

[0106] The topcoat of the antifouling and anticorrosive coating is prepared by mixing component A and component C in a dry container at a mass ratio of 1:2, and then applying it to the surface.

[0107] Example 3

[0108] Bio-based antifouling and anticorrosive coatings include a primer and a topcoat. The primer includes component A and component B; the topcoat includes component A and component C.

[0109] Component A, by weight: 30 parts castor oil, 26 parts polymethylene polyphenyl polyisocyanate, 0.3 parts triphenyl phosphite, 25 parts turpentine oil, and 7 parts monohydroxy polydimethylsiloxane (PDMS-OH).

[0110] Component B, by weight: 35 parts castor oil, 120 parts titanium dioxide.

[0111] Component C, by weight: 36 parts castor oil, 18 parts titanium dioxide, 19 parts 3-(2,3-epoxypropoxy)propyltrimethoxysilane, 8 parts nano zinc oxide, 5 parts nano silica, and 90 parts zinc phosphate.

[0112] Castor oil (Jinan Huamao Chemical Co., Ltd., refined castor oil), acid value 0.18mgKOH / g, hydroxyl value 180mgKOH / g.

[0113] The preparation process of component A is as follows: Triphenyl phosphite and castor oil are added to a reaction vessel and dehydrated at 115°C under a vacuum of 0.096 MPa for 1.8 hours. After dehydration, monohydroxy polydimethylsiloxane (PDMS-OH) is added to the vessel and stirred at 1050 rpm for 30 minutes. Then, polymethylene polyphenyl polyisocyanate and turpentine are added and thoroughly mixed. The temperature is adjusted to 45°C, and the stirring speed is maintained at 1050 rpm for half an hour. The temperature is then increased to 75°C at a rate of 3°C per minute and maintained at 75°C for 2 hours to carry out the polymerization reaction. After the reaction, the product is cooled to below 45°C, filtered through a wire mesh, and then sealed for storage.

[0114] The preparation process of component B is as follows: castor oil and titanium dioxide are placed in a mixing container and stirred at 1050 rpm for 30 minutes to prepare a premix. The premix is ​​then transferred to a three-roll mill for fine grinding and dispersion at 40 rpm for 2 hours to ensure sufficient shearing and dispersion, resulting in a uniform and fine paste. The final ground product has a fineness of 15 μm.

[0115] The preparation process of component C is as follows: castor oil, 3-(2,3-epoxypropoxy)propyltrimethoxysilane, and nano-silica are placed in a mixing container and stirred at 1050 rpm for 30 minutes to form a pre-dispersed material; then titanium dioxide, nano-zinc oxide, and zinc phosphate are added to the container and stirred at 1050 rpm for 60 minutes to form a uniform premix; finally, the premix is ​​transferred to a three-roll mill for fine grinding and dispersion at 40 rpm for 4 hours to ensure that the material undergoes sufficient shearing and dispersion to form a uniform and fine paste with a fineness of 15 μm.

[0116] The primer for the antifouling and anticorrosive coating is made by adding component B to component A at 15% of the mass of component A and stirring until homogeneous before application.

[0117] The topcoat of the antifouling and anticorrosive coating is prepared by mixing component A and component C in a dry container at a mass ratio of 1:2, and then applying it to the surface.

[0118] Example 4

[0119] Bio-based antifouling and anticorrosive coatings include a primer and a topcoat. The primer includes component A and component B; the topcoat includes component A and component C.

[0120] Component A, by weight: 33 parts castor oil, 28 parts polymethylene polyphenyl polyisocyanate, 0.4 parts triphenyl phosphite, 28 parts dimethyl carbonate, and 8 parts monohydroxy polydimethylsiloxane (PDMS-OH).

[0121] Component B, by weight: 38 parts castor oil, 125 parts iron oxide red.

[0122] Component C, by weight: 39 parts castor oil, 19 parts iron oxide red, 20 parts 3-(2,3-epoxypropoxy)propyltrimethoxysilane, 9 parts nano zinc oxide, 6 parts nano silica, and 95 parts mica iron oxide.

[0123] Castor oil (Jinan Huamao Chemical Co., Ltd., refined castor oil), acid value 0.2 mg KOH / g, hydroxyl value 185 mg KOH / g.

[0124] The preparation process of component A is as follows: Triphenyl phosphite and castor oil are added to a reaction vessel and dehydrated at 120°C under a vacuum of 0.096 MPa for 2 hours. After dehydration, monohydroxy polydimethylsiloxane (PDMS-OH) is added to the vessel and stirred at 1100 rpm for 30 minutes. Then, polymethylene polyphenyl polyisocyanate and dimethyl carbonate are added and thoroughly mixed. The temperature is adjusted to 45°C, and the stirring speed is 1100 rpm for half an hour. The temperature is then increased to 73°C at a rate of 3°C per minute and maintained at 73°C for 2 hours to carry out the polymerization reaction. After the reaction, the product is cooled to below 45°C, filtered through a wire mesh, and then sealed for storage.

[0125] The preparation process of component B is as follows: castor oil and iron oxide red are placed in a mixing container and stirred at 1100 rpm for 30 minutes to prepare a premix. The premix is ​​then transferred to a three-roll mill for fine grinding and dispersion at 40 rpm for 3 hours to ensure sufficient shearing and dispersion, resulting in a uniform and fine paste. The final ground product has a fineness of 16 μm.

[0126] The preparation process of component C is as follows: castor oil, 3-(2,3-epoxypropoxy)propyltrimethoxysilane, and nano-silica are placed in a mixing container and stirred at 1100 rpm for 30 minutes to form a pre-dispersed material; then iron oxide red, nano-zinc oxide, and mica iron oxide are added to the container and stirred at 1100 rpm for 60 minutes to form a uniform premix; finally, the premix is ​​transferred to a three-roll mill for fine grinding and dispersion treatment at 40 rpm for 3.7 hours to ensure that the material undergoes sufficient shearing and dispersion to form a uniform and fine paste with a fineness of 16 μm.

[0127] The primer for the antifouling and anticorrosive coating is made by adding component B to component A at 15% of the mass of component A and stirring until homogeneous before application.

[0128] The topcoat of the antifouling and anticorrosive coating is prepared by mixing component A and component C in a dry container at a mass ratio of 1:2, and then applying it to the surface.

[0129] Example 5

[0130] Bio-based antifouling and anticorrosive coatings include a primer and a topcoat. The primer includes component A and component B; the topcoat includes component A and component C.

[0131] Component A, by weight: 35 parts castor oil, 30 parts polymethylene polyphenyl polyisocyanate, 0.5 parts triphenyl phosphite, 30 parts dimethyl carbonate, and 8 parts monohydroxy polydimethylsiloxane (PDMS-OH).

[0132] Component B, by weight: 40 parts castor oil, 130 parts iron oxide red.

[0133] Component C, by weight: 40 parts castor oil, 20 parts iron oxide red, 22 parts 3-(2,3-epoxypropoxy)propyltrimethoxysilane, 10 parts nano zinc oxide, 6 parts nano silica, and 100 parts mica iron oxide.

[0134] Castor oil (Jinan Huamao Chemical Co., Ltd., refined castor oil), acid value 0.2 mg KOH / g, hydroxyl value 185 mg KOH / g.

[0135] The preparation process of component A is as follows: Triphenyl phosphite and castor oil are added to a reaction vessel and dehydrated at 120°C under a vacuum of 0.096 MPa for 2 hours. After dehydration, monohydroxy polydimethylsiloxane (PDMS-OH) is added to the vessel and stirred at 1000 rpm for 30 minutes. Then, polymethylene polyphenyl polyisocyanate and dimethyl carbonate are added and thoroughly mixed. The temperature is adjusted to 45°C, and the stirring speed is maintained at 1000 rpm for half an hour. Then, the temperature is increased to 75°C at a rate of 3°C per minute and maintained at 75°C for 2 hours to carry out the polymerization reaction. After the reaction, the product is cooled to below 45°C, filtered through a wire mesh, and then sealed for storage.

[0136] The preparation process of component B is as follows: castor oil and iron oxide red are placed in a mixing container and stirred at 1000 rpm for 30 minutes to prepare a premix. The premix is ​​then transferred to a three-roll mill for fine grinding and dispersion at 40 rpm for 3 hours to ensure sufficient shearing and dispersion, resulting in a uniform and fine paste. The final ground product has a fineness of 16 μm.

[0137] The preparation process of component C is as follows: castor oil, 3-(2,3-epoxypropoxy)propyltrimethoxysilane, and nano-silica are placed in a mixing container and stirred at 1000 rpm for 30 minutes to form a pre-dispersed material; then iron oxide red, nano-zinc oxide, and mica iron oxide are added to the container and stirred at 1000 rpm for 60 minutes to form a uniform premix; finally, the premix is ​​transferred to a three-roll mill for fine grinding and dispersion treatment at 40 rpm for 4 hours to ensure that the material undergoes sufficient shearing and dispersion to form a uniform and fine paste with a fineness of 16 μm.

[0138] The primer for the antifouling and anticorrosive coating is made by adding component B to component A at 15% of the mass of component A and stirring until homogeneous before application.

[0139] The topcoat of the antifouling and anticorrosive coating is prepared by mixing component A and component C in a dry container at a mass ratio of 1:2, and then applying it to the surface.

[0140] Performance Test Examples

[0141] Referring to the performance parameters in GB / T 6822-2014 "Antifouling and Anti-rust Coating System for Ships", JG / T 224-2007 "Anticorrosion Coatings for Steel Structures in Buildings", GB / T 1771-2007 "Determination of Neutral Salt Spray Resistance of Paints and Varnishes", and GB / T 5370-2007 "Shallow Sea Immersion Test Method for Antifouling Paint Samples", the antifouling and anti-corrosion coatings in the embodiments and comparative examples of this invention were tested, and the test results are summarized in Table 1. After aging tests, the main properties of the coatings are shown in Table 2.

[0142] Table 1. Test Results of Main Performance Indicators of Antifouling and Anticorrosion Coatings

[0143]

[0144] According to the data in Table 1, the performance of the antifouling and anticorrosion coatings of Examples 1-5 and Comparative Example 1 of the present invention all meet the standard requirements, and the performance of the antifouling and anticorrosion coatings of Examples 1-5 of the present invention is better than that of the antifouling and anticorrosion coating of Comparative Example 1. Among them, the adhesion, resistance to artificial aging and salt water resistance are significantly better than those of Comparative Example 1.

[0145] The antifouling and anticorrosion coatings of the above embodiments and comparative examples were artificially aged for 1000 hours to test their long-term protective performance.

[0146] Table 2. Test Results of Main Performance Indicators of Antifouling and Anticorrosion Coatings after 1000 hours of Aging

[0147]

[0148] According to the data in Table 2, the antifouling and anticorrosion coatings prepared in Examples 1-5 of this invention still meet the standard requirements after 1000 hours of artificial aging, exhibiting excellent performance indicators and achieving long-term protective effects. In contrast, the antifouling and anticorrosion coating in Comparative Example 1 showed a significant decrease in its main properties and poor long-term protective performance after artificial aging.

[0149] Compared with existing technologies, the bio-based antifouling and anticorrosion coating of the present invention has the following beneficial effects:

[0150] 1. By modifying the surface energy of low surface energy, compounding environmentally friendly antifouling agents and optimizing anticorrosive pigments, a triple effect of "physical anti-adhesion + chemical growth inhibition + corrosion protection" is achieved, which can simultaneously resist biological adhesion and media erosion, solving the problems of functional fragmentation and easy failure of traditional solutions.

[0151] 2. The raw materials used in this invention are biodegradable nano zinc oxide, chitosan-modified graphene oxide, castor oil, and other materials, which are green and environmentally friendly, comply with domestic and international environmental regulations, and have no ecological pollution risks during construction and service.

[0152] 3. Using castor oil as a key bio-based raw material to construct the coating matrix, replacing petroleum-based polyols, reduces dependence on non-renewable resources, endows the coating with good biocompatibility, and maintains the compatibility between the matrix and functional components, providing a green base for antifouling and anticorrosion functions.

[0153] 4. By chemically grafting low surface energy components and using complex coupling agents to strengthen interfacial bonding, the leaching of antifouling agents and coating cracking are reduced, ensuring that the coating maintains structural integrity and stable protective performance in dynamic service environments for a long time.

[0154] Therefore, this invention discloses a bio-based antifouling and anticorrosion coating to address the problems of poor functional synergy, insufficient environmental friendliness, and weak durability in existing antifouling and anticorrosion coatings. This antifouling and anticorrosion coating comprises a primer and a topcoat, using castor oil as the core raw material of a bio-based polyol. Component A achieves low surface energy modification by introducing monohydroxy polydimethylsiloxane (PDMS-OH). Component C is compounded with nano-zinc oxide, chitosan-modified graphene oxide, and nano-silica to form an environmentally friendly antifouling system. Through a synergistic mechanism of "low surface energy anti-adhesion + environmentally friendly antibacterial + passivation protection," it achieves integrated antifouling and anticorrosion functions. This coating is suitable for marine engineering, shipbuilding, and other fields, providing long-term protection for substrates.

[0155] In summary, the bio-based antifouling and anticorrosion coating of the present invention can achieve efficient synergy of antifouling and anticorrosion functions, green and environmentally friendly throughout the entire life cycle, and durable in dynamic service environments. It solves the core shortcomings of existing antifouling and anticorrosion coatings, meets the urgent needs of marine engineering and other fields for high-performance, low-pollution, and long-life protective materials, and is suitable for large-scale promotion and application.

[0156] In this specification, the invention has been described with reference to specific embodiments thereof. However, it will be apparent that various modifications and variations can be made without departing from the spirit and scope of the invention. Therefore, the specification and drawings should be considered illustrative rather than restrictive.

Claims

1. A bio-based antifouling and anticorrosive coating, comprising a primer and a topcoat, characterized in that, The primer comprises component A and component B, and the topcoat comprises component A and component C; The first component comprises 25 to 35 parts by weight of a first bio-based polyol, 20 to 30 parts by weight of polymethylene polyphenyl polyisocyanate, 0.1 to 0.5 parts by weight of triphenyl phosphite, 15 to 30 parts by weight of an environmentally friendly solvent, and 5 to 8 parts by weight of a low surface energy modifier. The B component comprises 30 to 40 parts by weight of the second bio-based polyol and 100 to 130 parts by weight of the first pigment; The C component comprises 30 to 40 parts by weight of a third bio-based polyol, 15 to 20 parts by weight of a second pigment, 15 to 22 parts by weight of a coupling agent, 5 to 10 parts by weight of an environmentally friendly antifouling agent, 3 to 6 parts by weight of a structural aid, and 80 to 100 parts by weight of an anticorrosive pigment.

2. The antifouling and anticorrosion coating based on bio-based materials according to claim 1, characterized in that, The first bio-based polyol, the second bio-based polyol, and the third bio-based polyol are all castor oil, the acid value of the castor oil is 0.1 mg KOH / g to 0.2 mg KOH / g, and the hydroxyl value of the castor oil is 160 mg KOH / g to 185 mg KOH / g.

3. The antifouling and anticorrosion coating based on bio-based materials according to claim 1, characterized in that, The environmentally friendly solvent is one of turpentine and dimethyl carbonate; the low surface energy modifier is monohydroxy polydimethylsiloxane; the first pigment and the second pigment are both one of iron oxide red and titanium dioxide; the coupling agent is 3-(2,3-epoxypropoxy)propyltrimethoxysilane; the environmentally friendly antifouling agent is one of nano zinc oxide and chitosan-modified graphene oxide; the structural aid is nano silica; or, the anticorrosive pigment is one of zinc phosphate and mica iron oxide.

4. The antifouling and anticorrosion coating based on bio-based materials according to claim 1, characterized in that, In the primer, the amount of component B added is 15% of the weight of component A; or, in the topcoat, the mass ratio of component A to component C is 1:

2.

5. A method for preparing an antifouling and anticorrosive coating based on bio-based materials according to claim 1, characterized in that, Includes the following steps: (1) Preparation of the A component (11) The first bio-based polyol and the triphenyl phosphite are subjected to dehydration treatment to obtain a dehydrated product; (12) The low surface energy modifier is added to the dehydrated product and stirred to obtain the stirred product; (13) Add the polymethylene polyphenyl polyisocyanate and the environmentally friendly solvent to the stirred product, mix thoroughly and evenly, then heat and stir, then heat and keep warm to carry out the polymerization reaction, and obtain the A component; (2) Preparation of the B component (21) Stir and mix the second bio-based polyol and the first pigment to obtain a premix; (22) The premix is ​​subjected to fine grinding and dispersion treatment to obtain component B; (3) Preparation of the C component (31) Stir and mix the third bio-based polyol, the coupling agent and the structural aid to obtain a pre-dispersion; (32) Add the second pigment, the environmentally friendly antifouling agent and the anticorrosive pigment to the pre-dispersed material and stir evenly to obtain a premixed material; (33) The premixed material is finely ground and dispersed to obtain component C; (4) Preparation of the primer Add component B to component A and stir until homogeneous; (5) Preparation of the topcoat Add component C to component A and stir until homogeneous.

6. The method for preparing the antifouling and anticorrosion coating based on bio-based materials according to claim 5, characterized in that, In step (11), the vacuum degree of the dehydration treatment is not less than 0.096 MPa, the temperature of the dehydration treatment is controlled within the range of 105℃ to 120℃, and the dehydration treatment lasts for more than 1.5 hours; in step (12), the stirring speed is 1000 rpm to 1100 rpm, and the stirring time is 30 minutes; or, in step (13), the heating and stirring speed is 1000 rpm to 1100 rpm, the heating and stirring temperature is 40℃ to 45℃, the heating and stirring time is half an hour, the heating rate is 3℃ per minute, the holding temperature is 70℃ to 75℃, and the holding time is 1.5 hours to 2 hours.

7. The method for preparing the antifouling and anticorrosion coating based on bio-based materials according to claim 5, characterized in that, In step (21), the stirring and mixing speed is 1000 to 1100 revolutions per minute, and the stirring and mixing time is 30 minutes; or, in step (22), the fine grinding and dispersing treatment speed is 40 revolutions per minute, and the fine grinding and dispersing treatment time is 2 to 3 hours.

8. The method for preparing the antifouling and anticorrosion coating based on bio-based materials according to claim 5, characterized in that, In step (31), the stirring speed is 1000 to 1100 revolutions per minute, and the stirring time is 30 minutes; in step (32), the stirring speed is 1000 to 1100 revolutions per minute, and the stirring time is 60 minutes; or, in step (33), the fine grinding and dispersion treatment speed is 40 revolutions per minute, and the fine grinding and dispersion treatment time is 3 to 4 hours.

9. The method for preparing the antifouling and anticorrosion coating based on bio-based materials according to claim 5, characterized in that, In step (41), the amount of component B added is 15% of the weight of component A; or, in step (51), the mass ratio of component A to component C is 1:

2.

10. A bio-based antifouling and anticorrosive coating, characterized in that, The antifouling and anticorrosive coating based on bio-based materials, as described in any one of claims 5 to 9, is prepared using this method.

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