A method for preparing an anticorrosive coating of a silicone-modified epoxy acrylate resin

Abstract

The application discloses a preparation method of an anticorrosive coating of a silicone-modified epoxy acrylate resin, and belongs to the technical field of material engineering. The coating contains component A and component B. The component A is prepared from methyl methacrylate base monomers, acrylate base monomers, glyceryl acrylate monomers, acrylate special function monomers, an initiator, a chain transfer agent and a solvent, the component B is prepared from silicone rubber and a crosslinking agent, and the mass ratio of the component A to the component B is 3-10:1. The two components are mixed and stirred, and then are coated on an electrode to be dried to obtain the coating. The coating has the characteristics of the epoxy resin, the acrylate resin and the silicone, compensates for the defects of single materials, has the performances of high adhesion, weather resistance, hydrophobicity and the like, can protect metals from corrosion for a long time through 180-day electrochemical experiment verification, and is suitable for metal corrosion protection.

Description

Technical Field

[0001] This invention belongs to the field of materials engineering technology, and particularly relates to a method for preparing an anti-corrosion coating of organosilicon-modified epoxy acrylic resin. Background Technology

[0002] Metal corrosion is a major challenge facing humanity's further exploration of the ocean. Compared to terrestrial environments, the corrosion rate of metals in the ocean is significantly higher. This not only leads to the gradual degradation of the functionality of related equipment but can also cause catastrophic accidents such as oil pipeline leaks and bridge collapses. Statistics show that global economic losses due to corrosion amount to trillions of dollars annually, a figure far exceeding the cumulative losses from various natural disasters.

[0003] To address this challenge, current research focuses on three main areas: first, surface modification techniques, such as nano-coatings and anodizing; second, electrochemical protection methods, including sacrificial anode methods and impressed current methods; and third, material design optimization, such as the development of highly corrosion-resistant alloys and composite materials.

[0004] Among numerous corrosion prevention methods, coating protection has become a research hotspot in this field due to its ease of operation and direct effects. Organic coatings, in particular, can directly protect metals through shielding, corrosion inhibition, and electrochemical effects, making them a key research focus. However, current organic coatings still suffer from problems such as weak adhesion, short service life, and inadequate protective performance. Summary of the Invention

[0005] Therefore, the present invention aims to develop an epoxy acrylate resin with strong adhesion, good protective properties, and long service life for corrosion protection of metal devices, thereby solving the aforementioned technical problems. Specifically, the present invention proposes a method for preparing an anti-corrosion coating of silicone-modified epoxy acrylate resin.

[0006] To achieve the above objectives, the present invention provides the following technical solution:

[0007] One of the objectives of this invention is to provide an anti-corrosion coating of silicone-modified epoxy acrylate resin, comprising component A (epoxy acrylate resin) and component B (silicone).

[0008] Component A is made from methacrylate basic monomers, acrylate basic monomers, glyceryl acrylate monomers, acrylic special functional monomers, initiators, chain transfer agents and solvents.

[0009] Component B is made from silicone rubber and crosslinking agent;

[0010] The mass ratio of component A to component B is (3-10):1.

[0011] Further, the mass ratio of the methacrylate base monomer, acrylate base monomer, glyceryl acrylate monomer, and acrylic special functional monomer is (4-6):(2-6):(0.1-1):(0.1-1); and / or,

[0012] The initiator is added in an amount of 10-20% of the total mass of all monomers; and / or,

[0013] The chain transfer agent is added in an amount of 0.5-2.0% of the total mass of all monomers; and / or,

[0014] The amount of solvent added is 80-120% of the total mass of all monomers.

[0015] Further, the methacrylate base monomer includes one or more of methyl methacrylate, ethyl methacrylate, hydroxyethyl methacrylate, isobutyl methacrylate, n-butyl methacrylate, isooctyl methacrylate, lauryl methacrylate, and octadecyl methacrylate; and / or,

[0016] The acrylate base monomers include one or more of methyl acrylate, ethyl acrylate, hydroxyethyl acrylate, isopropyl acrylate, n-butyl acrylate, isooctyl acrylate, lauryl acrylate, and octadecyl acrylate; and / or,

[0017] The glyceryl acrylate monomer includes one or more of glycidyl acrylate and glycidyl methacrylate; and / or,

[0018] The acrylic special functional monomers include one or more of cyclohexyl methacrylate, monofunctional extremely tough acrylate, and modified hydroxyethyl urea acrylate; and / or,

[0019] The initiator includes one or more of azobisisobutyronitrile, azobisisoheptanenitrile, dimethyl azobisisobutyrate, benzoyl peroxide, tert-butyl peroxide, methyl ethyl ketone peroxide, ammonium persulfate, and potassium persulfate; and / or,

[0020] The chain transfer agent includes one or more of n-dodecyl mercaptan, tert-dodecyl mercaptan, and aliphatic thiols; and / or,

[0021] The solvent includes one or more of toluene, xylene, n-butanol, butyl acetate, ethyl acetate, cyclohexanone, and methyl isobutyl ketone.

[0022] Furthermore, the preparation method of component A includes the following steps:

[0023] A monomer mixture is obtained by mixing methacrylate basic monomers, acrylate basic monomers, glyceryl acrylate monomers, and acrylic special functional monomers.

[0024] A mixture is obtained by adding a portion of solvent to the initiator and chain transfer agent;

[0025] The monomer mixture and the mixture were added to the remaining solvent in batches for dissolution. After heating, the mixture was stirred at a constant temperature to obtain a milky white, transparent, viscous epoxy acrylate resin.

[0026] The heating temperature is 70-100℃, and the constant temperature stirring time is 2-6 hours.

[0027] Furthermore, the mass ratio of the silicone rubber to the crosslinking agent is (10-100):(1-10).

[0028] Furthermore, the crosslinking agent is one or more of γ-aminopropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-methacryloyloxypropyltrimethoxysilane, and methyltriacetoxysilane.

[0029] Furthermore, the preparation method of component B includes the following steps: mixing and stirring silicone rubber with a crosslinking agent to achieve pre-crosslinking and obtain component B;

[0030] The stirring speed is 1000-3000 rpm and the stirring time is 10-20 min.

[0031] The second objective of this invention is to provide a method for preparing an anti-corrosion coating of silicone-modified epoxy acrylate resin, comprising the following steps: mixing and stirring component A and component B to obtain silicone-modified epoxy acrylate resin; coating the silicone-modified epoxy acrylate resin onto an electrode to form a coating, and drying it to obtain the anti-corrosion coating of silicone-modified epoxy acrylate resin.

[0032] Furthermore, the stirring speed is 1000-3000 rpm, the stirring time is 10-20 min, and the coating thickness is 50 μm.

[0033] The third objective of this invention is to provide an application of an organosilicon-modified epoxy acrylic resin anti-corrosion coating in metal corrosion protection coatings.

[0034] Compared with the prior art, the present invention has the following advantages and technical effects:

[0035] This invention successfully prepares a long-lasting corrosion-resistant coating by innovatively combining the properties of epoxy resin, acrylic resin, and organosilicon. Its core advantage lies in achieving complementary advantages and synergistic performance between different materials, specifically reflected in the following aspects:

[0036] First, the shortcomings of single materials are precisely compensated for. To address the poor weather resistance and brittleness of epoxy resin after long-term use, the excellent weather resistance of acrylic resin is utilized to improve it. The relatively weak corrosion resistance of acrylic resin is compensated for by the good corrosion resistance and high adhesion to the substrate of epoxy resin. Furthermore, the poor adhesion of silicone to the substrate is resolved by the strong adhesion properties of epoxy resin, thus freeing the coating from the performance limitations of a single material.

[0037] Secondly, it fully integrates the advantages of diverse materials. The coating retains the high adhesion and basic corrosion resistance of epoxy resin to the substrate, while also possessing the strong weather resistance of acrylic resin. Furthermore, it can be made multifunctional by introducing different monomers. At the same time, the good hydrophobic properties of organosilicon can effectively resist the intrusion of corrosive media (silicone rubber is transformed into organosilicon through crosslinking agents, which has good insulation and hydrophobicity). The superposition of multiple advantages makes the coating's protective performance more comprehensive.

[0038] Finally, experiments verified its long-term protective effect. By combining acrylate with epoxy resin and then with organosilicon to form a cross-polymer structure, combined with 180 days of electrochemical experiments, it was found that the coating can stably perform its anti-corrosion function, effectively solving the problem of metal parts being easily corroded in corrosive environments, and achieving long-term protection for metal parts. Attached Figure Description

[0039] The accompanying drawings, which form part of this invention, are used to provide a further understanding of the invention. The illustrative embodiments of the invention and their descriptions are used to explain the invention and do not constitute an undue limitation of the invention. In the drawings:

[0040] Figure 1 The infrared spectra of the organosilicon-modified epoxy acrylate resins prepared in Examples 1-3 are shown below.

[0041] Figure 2 The contact angle surface test diagrams are of the samples prepared in Examples 1-3 and Comparative Example 1;

[0042] Figure 3 This is a schematic diagram showing the samples prepared in Examples 1-3 and Comparative Example 1 after being soaked for 180 days.

[0043] Figure 4 The Nyquist plots are obtained by electrochemical testing of the samples prepared in Examples 1-3 and Comparative Example 1 after immersion for 180 days. Detailed Implementation

[0044] Various exemplary embodiments of the present invention will now be described in detail. This detailed description should not be considered as a limitation of the present invention, but rather as a more detailed description of certain aspects, features, and embodiments of the present invention.

[0045] It should be understood that the terminology used in this invention is merely for describing particular embodiments and is not intended to limit the invention. Furthermore, with respect to numerical ranges in this invention, it should be understood that each intermediate value between the upper and lower limits of the range is also specifically disclosed. Every smaller range between any stated value or intermediate value within a stated range, and any other stated value or intermediate value within said range, is also included in this invention. The upper and lower limits of these smaller ranges may be independently included or excluded from the range.

[0046] Unless otherwise stated, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art. While only preferred methods and materials have been described herein, any methods and materials similar or equivalent to those described herein may be used in the implementation or testing of this invention. All references to this specification are incorporated by way of citation to disclose and describe methods and / or materials associated with those references. In the event of any conflict with any incorporated reference, the content of this specification shall prevail.

[0047] Various modifications and variations can be made to the specific embodiments described in this specification without departing from the scope or spirit of the invention, as will be apparent to those skilled in the art. Other embodiments derived from this specification will also be obvious to those skilled in the art. This specification and embodiments are merely exemplary.

[0048] The terms “include,” “including,” “have,” “contain,” etc., used in this article are all open-ended terms, meaning that they include but are not limited to.

[0049] This invention provides a method for preparing an anti-corrosion coating of silicone-modified epoxy acrylate resin, comprising the following steps:

[0050] (1) Preparation of component A:

[0051] A monomer mixture is obtained by mixing methacrylate basic monomers, acrylate basic monomers, glyceryl acrylate monomers, and acrylic special functional monomers.

[0052] A mixture is obtained by adding a portion of solvent to the initiator and chain transfer agent;

[0053] The monomer mixture and the mixture were added to the remaining solvent in batches for dissolution. After heating, the mixture was stirred at a constant temperature to obtain a milky white, transparent, viscous epoxy acrylate resin.

[0054] The mass ratio of the partial solvent to the remaining solvent is 1:9;

[0055] The batching refers to dividing the monomer mixture and the mixture into 1-10 equal portions (e.g., 10 equal portions), and adding one portion of each to the remaining solvent every 10-20 minutes (e.g., 15 minutes) to ensure a complete reaction.

[0056] The heating temperature is 70-100℃ (e.g., 75℃ or 85℃), and the constant temperature stirring time is 2-6h (e.g., 3h).

[0057] (2) Preparation of component B: Silicone rubber and crosslinking agent are mixed in a mass ratio of (10-100):(1-10) (e.g., 100:1). The mixture is stirred at 1000-3000 rpm (e.g., 1000 rpm or 3000 rpm) for 10-20 min (e.g., 10 min) using a high-speed mixer to achieve pre-crosslinking and obtain component B.

[0058] (3) Mix component A and component B in a mass ratio of (3-10):1 (e.g., 3:1 or 10:1), and use a high-speed mixer to stir at a speed of 1000-3000 rpm (e.g., 1000 rpm or 3000 rpm) for 10-20 min (e.g., 10 min) until they are evenly mixed to obtain silicone-modified epoxy acrylic resin.

[0059] (4) The obtained silicone-modified epoxy acrylate resin is coated on the electrode to form a coating, and then dried to obtain the anti-corrosion coating of silicone-modified epoxy acrylate resin.

[0060] In the following optional embodiments of the present invention, in step (1), the mass ratio of the methacrylate base monomer, acrylate base monomer, glyceryl acrylate monomer, and acrylic special functional monomer is (4-6):(2-6):(0.1-1):(0.1-1). Exemplarily, in the following preferred embodiments of the present invention, the mass ratio of the methacrylate base monomer, acrylate base monomer, glyceryl acrylate monomer, and acrylic special functional monomer is 4:5:0.5:0.5 or 6:4:0.5:0.5.

[0061] In the following optional embodiments of the present invention, in step (1), the amount of initiator added is 10-20% of the total mass of all monomers; exemplaryly, in the following preferred embodiments of the present invention, the amount of initiator added is 10% of the total mass of all monomers.

[0062] In the following optional embodiments of the present invention, in step (1), the amount of chain transfer agent added is 0.5-2.0% of the total mass of all monomers; exemplaryly, in the following preferred embodiments of the present invention, the amount of chain transfer agent added is 1% of the total mass of all monomers.

[0063] In the following optional embodiments of the present invention, in step (1), the amount of solvent added is 80-120% of the total mass of all monomers. Exemplarily, in the following preferred embodiments of the present invention, the amount of solvent added is 91% or 100% of the total mass of all monomers.

[0064] In the following optional embodiments of the present invention, in step (1), the methacrylate base monomer includes one or more of methyl methacrylate, ethyl methacrylate, hydroxyethyl methacrylate, isobutyl methacrylate, n-butyl methacrylate, isooctyl methacrylate, lauryl methacrylate, and octadecyl methacrylate; for example, in the following preferred embodiments of the present invention, the methacrylate base monomer is methyl methacrylate.

[0065] In the following optional embodiments of the present invention, in step (1), the acrylate base monomer includes one or more of methyl acrylate, ethyl acrylate, hydroxyethyl acrylate, isopropyl acrylate, n-butyl acrylate, isooctyl acrylate, lauryl acrylate and octadecyl acrylate; for example, in the following preferred embodiments of the present invention, the acrylate base monomer is a mixture of ethyl acrylate and n-butyl acrylate.

[0066] In the following optional embodiments of the present invention, in step (1), the glyceryl acrylate monomer includes one or more of glycidyl acrylate and glycidyl methacrylate; exemplaryly, in the following preferred embodiments of the present invention, the glyceryl acrylate monomer is glycidyl methacrylate.

[0067] In the following optional embodiments of the present invention, in step (1), the special functional monomer of acrylic acid includes one or more of cyclohexyl methacrylate, monofunctional extremely tough acrylate and modified hydroxyethyl urea acrylate; for example, in the following preferred embodiments of the present invention, the special functional monomer of acrylic acid is modified hydroxyethyl urea acrylate.

[0068] In the following optional embodiments of the present invention, in step (1), the initiator includes one or more of azobisisobutyronitrile, azobisisoheptanenitrile, dimethyl azobisisobutyrate, benzoyl peroxide, tert-butyl peroxide, methyl ethyl ketone peroxide, ammonium persulfate, and potassium persulfate; exemplaryly, in the following preferred embodiments of the present invention, the initiator is azobisisobutyronitrile.

[0069] In the following optional embodiments of the present invention, in step (1), the chain transfer agent includes one or more of n-dodecyl mercaptan, tert-dodecyl mercaptan and aliphatic thiols; exemplaryly, in the following preferred embodiments of the present invention, the chain transfer agent is n-dodecyl mercaptan.

[0070] In the following optional embodiments of the present invention, in step (1), the solvent includes one or more of toluene, xylene, n-butanol, butyl acetate, ethyl acetate, cyclohexanone, and methyl isobutyl ketone. Exemplarily, in the following preferred embodiments of the present invention, the solvent is butyl acetate.

[0071] In the following optional embodiments of the present invention, in step (2), the crosslinking agent is one or more of γ-aminopropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-methacryloyloxypropyltrimethoxysilane, and methyltriacetoxysilane. Exemplarily, in the following preferred embodiments of the present invention, the crosslinking agent is methyltriacetoxysilane.

[0072] In the following optional embodiments of the present invention, in step (4), the thickness of the coating is 50 μm, the spin coater speed is 200 rpm and the time is 3 s; the electrode is a Q235 carbon steel sheet with an exposed size of 10 mm × 10 mm.

[0073] An anti-corrosion coating of organosilicon-modified epoxy acrylate resin can be prepared using the above preparation method.

[0074] The anti-corrosion coating of the silicone-modified epoxy acrylate resin can be applied to metal corrosion protection coatings.

[0075] Unless otherwise specified, the term "parts" in this invention refers to parts by weight.

[0076] All raw materials used in this invention were purchased from the market.

[0077] The technical solution of the present invention will be further illustrated by the following embodiments.

[0078] Example 1

[0079] A method for preparing an anti-corrosion coating of silicone-modified epoxy acrylic resin, comprising the following steps:

[0080] (1) Preparation of component A:

[0081] Monomers: Take 4 parts methyl methacrylate, 2 parts ethyl acrylate, 3 parts n-butyl acrylate, 0.5 parts glycidyl methacrylate, and 0.5 parts modified hydroxyethyl urea acrylate;

[0082] Initiator: Azobisisobutyronitrile, the amount used is 10% of the total mass of all monomers, i.e., 1 part;

[0083] Chain transfer agent: n-dodecyl mercaptan, used at 1% of the total mass of all monomers, i.e., 0.1 parts;

[0084] Solvent: Butyl acetate, used in an amount of 100% of the total mass of all monomers, i.e., 10 parts;

[0085] 1) Take 4 parts of methyl methacrylate, 2 parts of ethyl acrylate, 3 parts of n-butyl acrylate, 0.5 parts of glycidyl methacrylate and 0.5 parts of modified hydroxyethyl urea acrylate in a 500mL beaker, and use a stirring rod to mix the various monomers evenly to obtain a monomer mixture;

[0086] 2) Take 1 part butyl acetate, add 1 part azobisisobutyronitrile and 0.1 part n-dodecyl mercaptan, stir well to obtain a mixture;

[0087] 3) Divide the monomer mixture obtained in step 1) and the mixture obtained in step 2) into 10 equal portions. Take 1 portion of the monomer mixture and 1 portion of the mixture and add them simultaneously to a 1L three-necked flask containing the remaining 9 portions of butyl acetate (nitrogen gas is always introduced into the three-necked flask to ensure that it is in a nitrogen atmosphere during the reaction). Turn on the heating switch, stirring device and condenser. Set the oil bath heating temperature to 75℃ and the stirring speed to 1200r / min. Check that the liquid level in the three-necked flask is lower than the liquid level in the oil bath. Maintain heating and stirring. When the temperature in the oil bath reaches 75℃, maintain heating for 15min. Then, add the remaining 9 portions of monomer mixture and 9 portions of mixture to the three-necked flask in batches, with each batch added 15min apart. Keep the temperature and stir for 15min for each batch. After all the raw materials have been added, keep the temperature at 75℃ and stir for 3h to obtain a milky white, transparent and viscous epoxy acrylic resin, i.e., component A.

[0088] (2) Preparation of component B:

[0089] Crosslinking agent: methyltriacetoxysilane;

[0090] At 25°C, 100 parts of silicone rubber and 1 part of methyltriacetoxysilane were mixed and stirred at 3000 rpm for 10 min using a high-speed mixer to achieve pre-crosslinking and obtain component B.

[0091] (3) Mix component A and component B in a mass ratio of 10:1 and stir at 3000 rpm for 10 minutes using a high-speed mixer until the mixture is homogeneous to obtain silicone-modified epoxy acrylic resin.

[0092] (4) The silicone-modified epoxy acrylate resin was coated onto the prepared Q235 carbon steel sheet electrode using a spin coater at a speed of 200 rpm and a time of 3 s. The exposed size of the carbon steel sheet was 10 mm × 10 mm. After coating, the electrode was placed in a 40℃ oven and left to stand for 7 days to obtain the silicone-modified epoxy acrylate resin coating. The coating thickness was measured to be about 50 μm by a paint film thickness gauge.

[0093] Example 2

[0094] Same as Example 1, except that in step (3), component A and component B are mixed in a mass ratio of 3:1.

[0095] Example 3

[0096] A method for preparing an anti-corrosion coating of silicone-modified epoxy acrylic resin, comprising the following steps:

[0097] (1) Preparation of component A:

[0098] Monomers: Take 6 parts methyl methacrylate, 2 parts ethyl acrylate, 2 parts n-butyl acrylate, 0.5 parts glycidyl methacrylate, and 0.5 parts modified hydroxyethyl urea acrylate;

[0099] Initiator: Azobisisobutyronitrile, used in an amount of 10% of the total mass of all monomers, i.e., 1.1 parts;

[0100] Chain transfer agent: n-dodecyl mercaptan, used at 1% of the total mass of all monomers, i.e., 0.11 parts;

[0101] Solvent: Butyl acetate, used in an amount of 91% of the total mass of all monomers, i.e., 10 parts;

[0102] 1) Take 6 parts of methyl methacrylate, 2 parts of ethyl acrylate, 2 parts of n-butyl acrylate, 0.5 parts of glycidyl methacrylate and 0.5 parts of modified hydroxyethyl urea acrylate in a 500mL beaker, and use a stirring rod to mix the various monomers evenly to obtain a monomer mixture;

[0103] 2) Take 1.32 parts of butyl acetate, add 1.1 parts of azobisisobutyronitrile and 0.11 parts of n-dodecyl mercaptan, stir well to obtain a mixture;

[0104] 3) Divide the monomer mixture obtained in step 1) and the mixture obtained in step 2) into 10 equal portions. Take 1 portion of the monomer mixture and 1 portion of the mixture and add them simultaneously to a 1L three-necked flask containing the remaining 11.88 portions of butyl acetate (nitrogen gas is always introduced into the three-necked flask to ensure that it is in a nitrogen atmosphere during the reaction). Turn on the heating switch, stirring device and condenser. Set the oil bath heating temperature to 85℃ and the stirring speed to 1200r / min. Check that the liquid level in the three-necked flask is lower than the liquid level in the oil bath. Maintain heating and stirring. When the temperature in the oil bath reaches 85℃, maintain heating for 15min. Then, add the remaining 9 portions of monomer mixture and 9 portions of mixture to the three-necked flask in batches, with each batch added 15min apart. Keep the temperature and stir for 15min for each batch. After all the raw materials have been added, keep the temperature at 85℃ and stir for 3h to obtain a milky white, transparent and viscous epoxy acrylic resin, i.e., component A.

[0105] (2) Preparation of component B:

[0106] Crosslinking agent: methyltriacetoxysilane;

[0107] At 25°C, 100 parts of silicone rubber and 1 part of methyltriacetoxysilane were mixed and stirred at 1000 rpm for 10 min using a high-speed mixer to achieve pre-crosslinking and obtain component B.

[0108] (3) Mix component A and component B in a mass ratio of 10:1, and stir at 1000 rpm for 10 min using a high-speed mixer until the mixture is homogeneous to obtain silicone-modified epoxy acrylic resin.

[0109] (4) The silicone-modified epoxy acrylate resin was coated onto the prepared Q235 carbon steel sheet electrode using a spin coater at a speed of 200 rpm and a time of 3 s. The exposed size of the carbon steel sheet was 10 mm × 10 mm. After coating, the electrode was placed in a 40℃ oven and left to stand for 7 days to obtain the silicone-modified epoxy acrylate resin coating. The coating thickness was measured to be about 50 μm by a paint film thickness gauge.

[0110] Comparative Example 1

[0111] A method for preparing an anti-corrosion coating, comprising the following steps:

[0112] (1) Preparation of component A:

[0113] Monomers: Take 4 parts methyl methacrylate, 2 parts ethyl acrylate, 3 parts n-butyl acrylate, 0.5 parts glycidyl methacrylate, and 0.5 parts modified hydroxyethyl urea acrylate;

[0114] Initiator: Azobisisobutyronitrile, the amount used is 10% of the total mass of all monomers, i.e., 1 part;

[0115] Chain transfer agent: n-dodecyl mercaptan, used at 1% of the total mass of all monomers, i.e., 0.1 parts;

[0116] Solvent: Butyl acetate, used in an amount of 100% of the total mass of all monomers, i.e., 10 parts;

[0117] 1) Take 4 parts of methyl methacrylate, 2 parts of ethyl acrylate, 3 parts of n-butyl acrylate, 0.5 parts of glycidyl methacrylate and 0.5 parts of modified hydroxyethyl urea acrylate in a 500mL beaker, and use a stirring rod to mix the various monomers evenly to obtain a monomer mixture;

[0118] 2) Take 1 part butyl acetate, add 1 part azobisisobutyronitrile and 0.1 part n-dodecyl mercaptan, stir well to obtain a mixture;

[0119] 3) Divide the monomer mixture obtained in step 1) and the mixture obtained in step 2) into 10 equal portions. Take 1 portion of the monomer mixture and 1 portion of the mixture and add them simultaneously to a 1L three-necked flask containing the remaining 9 portions of butyl acetate (nitrogen gas is always introduced into the three-necked flask to ensure that it is in a nitrogen atmosphere during the reaction). Turn on the heating switch, stirring device and condenser. Set the oil bath heating temperature to 75℃ and the stirring speed to 1200r / min. Check that the liquid level in the three-necked flask is lower than the liquid level in the oil bath. Maintain heating and stirring. When the temperature in the oil bath reaches 75℃, maintain heating for 15min. Then, add the remaining 9 portions of monomer mixture and 9 portions of mixture to the three-necked flask in batches, with each batch added 15min apart. Keep the temperature and stir for 15min for each batch. After all the raw materials have been added, keep the temperature at 75℃ and stir for 3h to obtain a milky white, transparent and viscous epoxy acrylic resin, i.e., component A.

[0120] (2) Component A was coated onto a pre-prepared Q235 carbon steel sheet electrode using a spin coater at a speed of 200 rpm and a time of 3 s. The exposed size of the carbon steel sheet was 10 mm × 10 mm. After coating, the electrode was placed in a 40 ℃ oven and left to stand for 7 days to obtain the coating. The coating thickness was measured to be about 50 μm by a paint film thickness gauge.

[0121] Figure 1 The infrared spectra of the organosilicon-modified epoxy acrylate resins prepared in Examples 1-3 are shown below. Figure 1 As can be seen from the data, the infrared absorption line of the resin containing modified hydroxyethyl urea acrylate is at 3520 cm⁻¹. -1 There is a distinct absorption peak at 1726 cm⁻¹, which is the absorption peak of secondary amide. -1 The strong absorption peak at 1022 cm⁻¹ is the stretching vibration peak of the associated C=O bond. -1 The position is a symmetric stretching vibration of the COC group, 1147-1237 cm⁻¹. -1 The point is the asymmetric stretching vibration of the COC group, 1382 cm⁻¹. -1 The peak at 910 cm⁻¹ is the angle-shifting vibration peak of the -CH bond. -1 The presence of absorption peaks for epoxy groups indicates that the introduction of epoxy groups into the epoxy acrylic resin was successful.

[0122] Performance testing:

[0123] The samples prepared in Examples 1-3 and Comparative Example 1 were immersed in a 3.5 wt% NaCl solution for 180 days for electrochemical impedance spectroscopy. The results are as follows: Figure 2 As shown. By Figure 2It can be seen that the contact angle of Comparative Example 1 is 95°, while the contact angle of Examples 1-3, after the addition of component B, is significantly increased, resulting in a more hydrophobic surface. A hydrophobic surface can increase resistance to corrosive media. Therefore, after immersion in a 3.5 wt% NaCl solution for 180 days, the silicone-modified epoxy acrylate resin coating still exhibits good corrosion resistance.

[0124] Figure 3 This is a schematic diagram showing the samples prepared in Examples 1-3 and Comparative Example 1 after being soaked for 180 days. Figure 3 As can be seen, after the four sets of electrodes were immersed in a 3.5 wt% sodium chloride solution for 180 days, Comparative Example 1 was severely corroded, while Examples 1, 2, and 3 still had good corrosion resistance, ensuring that the substrate was not corroded.

[0125] Figure 4 The Nyquist plots are obtained from electrochemical tests of the samples prepared in Examples 1-3 and Comparative Example 1 after immersion for 180 days. Figure 4 As can be seen, after 180 days, Examples 1, 2, and 3 still exhibited high electrochemical impedance values, indicating that they could still provide corrosion protection for the substrate. However, Comparative Example 1 showed a significantly lower electrochemical impedance value after 180 days of immersion compared to the other three groups, indicating that it had lost its corrosion protection function.

[0126] The above are merely preferred embodiments of the present invention, but the scope of protection of the present invention is not limited thereto. Any variations or substitutions that can be easily conceived by those skilled in the art within the scope of the technology disclosed in the present invention should be included within the scope of protection of the present invention. Therefore, the scope of protection of the present invention should be determined by the scope of the claims.

Claims

1. A silicone-modified epoxy acrylic resin anti-corrosion coating, characterized in that, The method for preparing the anti-corrosion coating of the silicone-modified epoxy acrylate resin includes the following steps: mixing and stirring component A and component B to obtain silicone-modified epoxy acrylate resin; coating the silicone-modified epoxy acrylate resin onto the electrode to form a coating, and drying it to obtain the anti-corrosion coating of the silicone-modified epoxy acrylate resin. Component A is made from methacrylate basic monomers, acrylate basic monomers, glycidyl acrylate monomers, acrylic special functional monomers, initiators, chain transfer agents and solvents. The methacrylate base monomers include one or more of methyl methacrylate, ethyl methacrylate, hydroxyethyl methacrylate, isobutyl methacrylate, n-butyl methacrylate, isooctyl methacrylate, lauryl methacrylate, and octadecyl methacrylate. The acrylate base monomers include one or more of methyl acrylate, ethyl acrylate, hydroxyethyl acrylate, isopropyl acrylate, n-butyl acrylate, isooctyl acrylate, lauryl acrylate, and octadecyl acrylate. The glycidyl acrylate monomer is one or more of glycidyl acrylate and glycidyl methacrylate; The special functional monomer of acrylic acid is modified hydroxyethyl urea acrylate; The solvent includes one or more of toluene, xylene, n-butanol, butyl acetate, ethyl acetate, cyclohexanone, and methyl isobutyl ketone; The mass ratio of the methacrylate base monomer, acrylate base monomer, glycidyl acrylate monomer, and acrylic special functional monomer is (4-6):(2-6):(0.1-1):(0.1-1). Component B is made from silicone rubber and a crosslinking agent; the mass ratio of the silicone rubber to the crosslinking agent is (10-100):1; the crosslinking agent is methyltriacetoxysilane. The preparation method of component B includes the following steps: mixing and stirring silicone rubber with a crosslinking agent to achieve pre-crosslinking and obtain component B; the stirring speed of mixing and stirring the silicone rubber with the crosslinking agent is 1000-3000 rpm and the stirring time is 10-20 min. The mass ratio of component A to component B is (3-10):

1.

2. The anti-corrosion coating of organosilicon-modified epoxy acrylic resin according to claim 1, characterized in that, The amount of the initiator added is 10-20% of the total mass of all monomers; The chain transfer agent is added in an amount of 0.5-2.0% of the total mass of all monomers; The amount of solvent added is 80-120% of the total mass of all monomers.

3. The anti-corrosion coating of organosilicon-modified epoxy acrylic resin according to claim 2, characterized in that, The initiator includes one or more of azobisisobutyronitrile, azobisisoheptanenitrile, dimethyl azobisisobutyrate, benzoyl peroxide, tert-butyl peroxide, methyl ethyl ketone peroxide, ammonium persulfate, and potassium persulfate. The chain transfer agent includes one or more of n-dodecyl mercaptan and tert-dodecyl mercaptan.

4. The anti-corrosion coating of silicone-modified epoxy acrylic resin according to claim 1, characterized in that, The preparation method of component A includes the following steps: A monomer mixture is obtained by mixing methacrylate basic monomers, acrylate basic monomers, glycidyl acrylate monomers, and acrylic special functional monomers. A mixture is obtained by adding a portion of solvent to the initiator and chain transfer agent; The monomer mixture and the mixture were added to the remaining solvent in batches for dissolution, heated in a nitrogen atmosphere, and stirred at a constant temperature after heating to obtain component A; The heating temperature is 70-100℃, and the constant temperature stirring time is 2-6 hours.

5. A method for preparing an anti-corrosion coating of organosilicon-modified epoxy acrylate resin as described in any one of claims 1-4, characterized in that, The process includes the following steps: mixing and stirring component A and component B to obtain silicone-modified epoxy acrylate resin; The silicone-modified epoxy acrylate resin is coated onto the electrode to form a coating, and then dried to obtain the silicone-modified epoxy acrylate resin anti-corrosion coating.

6. The preparation method according to claim 5, characterized in that, The mixing and stirring of component A and component B is carried out at a stirring speed of 1000-3000 rpm for 10-20 min; the coating thickness is 50 μm.

7. The application of an anti-corrosion coating of silicone-modified epoxy acrylate resin as described in any one of claims 1-4 in metal corrosion protection coatings.

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