A bio-based epoxy resin, its preparation method, and a highly sealed, environmentally friendly anti-corrosion coating

Abstract

This invention provides a bio-based epoxy resin, its preparation method, and a highly sealing, environmentally friendly anti-corrosion coating. The bio-based epoxy resin has the following general structural formula: R1 is selected from one or a combination of hydrogen atoms, alkyl groups, and alkyl carbonyl esters; R2 and R3 are each independently selected from one or a combination of hydrogen atoms and alkyl groups; a, b, and c are each independently selected from any integer from 1 to 20; and h, f, and g are each independently selected from any integer from 1 to 3. The highly sealing, environmentally friendly anti-corrosion coating of this invention exhibits good sealing properties, anti-sagging, anti-settling, and long-lasting anti-corrosion performance.

Description

Technical Field

[0001] This invention relates to the field of anti-corrosion coating technology, and more specifically, to a bio-based epoxy resin, its preparation method, and a highly sealed environmentally friendly anti-corrosion coating. Background Technology

[0002] Marine facilities located in nearshore and deep-sea areas, such as artificial islands, fixed oil and gas production platforms, floating oil and gas production platforms, subsea oil production units, subsea oil and gas pipelines, and FPSOs, are subjected to harsh marine environments with high humidity, high salinity, ultraviolet radiation, rain erosion, large diurnal temperature variations, and wave impact. This places higher demands on protective coating systems. The anti-corrosion primer, in particular, needs to have the same lifespan as the marine facility to reduce the frequency of repairs and lower the difficulty of later maintenance. In recent years, anti-corrosion coatings used in outdoor petrochemical facilities, bridge steel structures, and other fields have also been required to have a long lifespan, extending maintenance cycles and aiming to achieve the same lifespan as the facility itself.

[0003] Currently, the most widely used heavy-duty anti-corrosion coatings are thick-film type. To meet the low viscosity requirements for application, they typically have high VOC content, low single-coat thickness, and long application cycles. They cannot simultaneously achieve the requirements of high solids content, low viscosity, high film thickness, anti-sagging, and anti-settling. Summary of the Invention

[0004] To address the aforementioned problems, this invention provides a bio-based epoxy resin that exhibits good sealing properties, anti-sagging, anti-settling properties, and long-lasting anti-corrosion performance when used in anti-corrosion coatings.

[0005] Firstly, one of the objectives of this invention is to provide a bio-based epoxy resin.

[0006] Specifically, the general structural formula of the bio-based epoxy resin is as follows.

[0007] in, R1 is selected from one or a combination of hydrogen atoms, alkyl groups, and alkyl carbonyl esters; wherein the alkyl group or alkyl carbonyl ester is selected from alkyl groups having 1-10 carbon atoms, alkyl carbonyl esters having 1-10 carbon atoms, preferably from alkyl groups having 2-8 carbon atoms, alkyl carbonyl esters having 2-8 carbon atoms. R2 and R3 are each independently selected from one or a combination of hydrogen atoms and alkyl groups; preferably from one or a combination of alkyl groups having 1 to 8 carbon atoms; more preferably from one or a combination of alkyl groups having 1 to 5 carbon atoms. a, b, and c are each independently selected from any integer from 1 to 20; preferably from any integer from 2 to 10; more preferably from any integer from 3 to 5. h, f, and g are each independently selected from any integer from 1 to 3; preferably from any integer from 1 to 2.

[0008] The bio-based epoxy resin provided by the present invention has multiple functions, preferably 2-12 functions, more preferably 4-8 functions, and can improve the performance of coatings when applied to coatings.

[0009] In a preferred embodiment of the present invention, the general structural formula of the bio-based epoxy resin is as follows:

[0010] The aforementioned bio-based epoxy resin is a hexafunctional epoxy resin. When applied to coatings, it can significantly improve the sealing properties of highly sealed environmentally friendly anti-corrosion coatings, thereby enhancing the anti-corrosion properties of the coatings.

[0011] Secondly, another objective of this invention is to provide a method for preparing a bio-based epoxy resin, which is one of the objectives of this invention.

[0012] Specifically, the preparation method includes the following steps: The raw materials, including secondary amine derivatives containing phenolic hydroxyl groups and diisocyanate derivatives, are reacted, and then epoxy derivatives are added to react again to obtain bio-based epoxy resin.

[0013] More specifically, the preparation method includes the following steps: Step 1: Disperse the secondary amine derivative containing phenolic hydroxyl groups in a solvent, add the diisocyanate derivative at low temperature to react, and obtain the first intermediate; Step 2: Add epoxy derivatives and react under alkaline conditions to obtain bio-based epoxy resin.

[0014] Specifically, the preparation method includes the following steps: Step 1: Under high-speed dispersion, the secondary amine derivative containing phenolic hydroxyl groups is dispersed in a solvent (such as ethyl acetate). Under the protection of an inert gas (such as N2), the temperature is lowered to 0-20°C, and the diisocyanate derivative is added dropwise. The reaction is carried out for 1-2 hours to obtain the first intermediate. Step 2: Under the protection of an inert gas (such as N2), the epoxy derivative is added under high-speed dispersion, the temperature is raised to 50-75°C, an alkaline solution is added dropwise, the reaction is carried out for 1-3 hours, the temperature is raised to 80-90°C, the reaction is carried out for 4-6 hours, the temperature is lowered to room temperature, the mixture is washed with water until neutral, and the solvent and unreacted monomers are removed by vacuum distillation to obtain the bio-based epoxy resin.

[0015] Preferably, the molar ratio of the phenolic hydroxyl-containing secondary amine derivative, diisocyanate derivative, and epoxy derivative is 1:(0.5~0.6):(9~12), more preferably 1:(0.55~0.6):(9~10.5).

[0016] Preferably, the molar ratio of the epoxy derivative to the base is 1:(0.90-1.05).

[0017] Preferably, the alkali is selected from sodium hydroxide.

[0018] Furthermore, the general structural formula of secondary amine derivatives containing phenolic hydroxyl groups is as follows:

[0019] R2 and R3 are each independently selected from one or a combination of hydrogen atoms and alkyl groups, wherein the alkyl group is selected from alkyl groups having 1 to 8 carbon atoms, preferably from alkyl groups having 1 to 5 carbon atoms; b and c are each independently selected from any integer from 1 to 20, preferably from any integer from 2 to 10, and more preferably from any integer from 3 to 5; The f and g are each independently selected from any integer from 1 to 3, preferably from any integer from 1 to 2.

[0020] In a preferred embodiment of the present invention, the secondary amine derivative containing a phenolic hydroxyl group is selected from dobutamine.

[0021] Furthermore, the general structural formula of the diisocyanate derivative is as follows:

[0022] R1 is selected from one or a combination of hydrogen atoms, alkyl groups, and alkyl carbonyl esters; wherein the alkyl group and alkyl carbonyl ester are selected from alkyl groups having 1-10 carbon atoms, alkyl carbonyl esters having 1-10 carbon atoms, preferably from alkyl groups having 2-8 carbon atoms, alkyl carbonyl esters having 2-8 carbon atoms. The a is selected from any integer from 1 to 20, preferably from any integer from 2 to 10, and more preferably from any integer from 3 to 5.

[0023] In a preferred embodiment of the present invention, the diisocyanate derivative is selected from one or a combination of L-lysine diisocyanate and hexamethylene diisocyanate.

[0024] Furthermore, the general structural formula of epoxy derivatives is as follows:

[0025] The h is selected from any integer from 1 to 3, preferably from any integer from 1 to 2; the X is selected from halogens, preferably from chlorine.

[0026] In a preferred embodiment of the present invention, the epoxy derivative is selected from epichlorohydrin.

[0027] Thirdly, the objective of this invention is to provide a highly sealed, environmentally friendly, and corrosion-resistant coating.

[0028] Specifically, the coating comprises epoxy resin; wherein the epoxy resin is selected from one or more of the following: bio-based epoxy resin of one purpose of the present invention, or bio-based epoxy resin of one purpose of the present invention combined with BPA-type epoxy resin, polyurethane-modified epoxy resin, acrylic-modified epoxy resin, hydrogenated epoxy resin, and bio-based epoxy resin, wherein the bio-based epoxy resin accounts for at least 20% of the total mass of the epoxy resin, preferably at least 30%.

[0029] It is worth mentioning that after the bio-based epoxy resin, which is one of the objectives of this invention, is prepared by the preparation method of the second objective of this invention, propylene glycol methyl ether acetate needs to be added to adjust the solid content, that is, to prepare a bio-based epoxy resin with a solid content of 50-70% for later use.

[0030] Furthermore, the aforementioned highly sealing environmentally friendly anti-corrosion coating includes component A and component B, wherein component A and component B are respectively formulated from raw materials comprising the following components: Component A, by weight parts: 100 parts by weight of epoxy resin; 20-80 parts by weight of reactive diluent, preferably 30-60 parts by weight; The anti-settling agent is 1-10 parts by weight, preferably 2-8 parts by weight; The rust-inhibiting filler is 20-60 parts by weight, preferably 30-50 parts by weight; The pigments and fillers are 100-220 parts by weight, preferably 120-200 parts by weight; 1-15 parts by weight of the additive, preferably 2-10 parts by weight; Component B, by weight: 100 parts by weight of epoxy curing agent; 0-6 parts by weight of curing accelerator, preferably 0-5 parts by weight; The weight ratio of component A to component B is (6-12):1, preferably (6-10):1.

[0031] Further, the active diluent is selected from one or a combination of aliphatic or alicyclic difunctional or trifunctional glycidyl ethers or glycidyl esters; preferably from triethylene glycol diglycidyl ether, ethylene glycol diglycidyl ether, diglycidyl ether, adipic acid diglycidyl ester, bis(7-oxabicyclo[4.1.0]3-heptylmethyl) adipate, cyclohexane-1,2-dicarboxylic acid diglycidyl ester, glycerol triglycidyl ether, 2,2'-[(1-methylethylidene)bis(4,1-cyclohexyloxymethylene)]bis(ethylene oxide), 1,4-bis[(glycidyloxy)methyl]cyclohexane The active diluent is selected from one or a combination of the following: alkylene, 1,4-cyclohexanediethanol diglycidyl ether, propylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, polyethylene glycol diglycidyl ether, glycerol diglycidyl ether, poly(propylene glycol) diglycidyl ether, glycerol propoxy triglycidyl ether, 1,2-cyclohexanediol diglycidyl ether, polyethylene glycol diglycidyl ether, 2,2-bis[(epoxyethylene methoxy)methyl]propane-1,3-diol, dipropylene glycol diglycidyl ether, trimethylolethane triglycidyl ether, and 3-[bis(glycidyloxymethyl)methoxy]-1,2-propanediol. These active diluents are used to reduce the viscosity of coating systems and improve the flexibility of cured anti-corrosion coatings.

[0032] Furthermore, the anti-settling agent is selected from one or a combination of organobentonite, attapulgite, lithium magnesium silicate, wax powder, polyamide wax, fumed silica, hydrogenated castor oil and its derivatives, modified polyurea solution, titanate coupling agent, polyhydroxycarboxylic acid amide solution, and montmorillonite. The above-mentioned anti-settling agents can improve the settling grade of the coating, enhance its anti-sagging properties, thereby increasing the thickness of a single coat, reducing the number of applications, and shortening the construction cycle.

[0033] Furthermore, the rust-inhibiting filler is selected from one or a combination of zinc phosphate, modified zinc phosphate, composite zinc phosphate, aluminum tripolyphosphate, modified aluminum tripolyphosphate, calcium phosphate, zinc aluminum phosphate, zinc aluminum molybdenum phosphate, strontium aluminum polyphosphate, zinc molybdenum polyphosphate, calcium aluminum polyphosphate, calcium phosphosilicate, strontium phosphosilicate, barium phosphosilicate, zinc strontium phosphosilicate, calcium strontium phosphosilicate, zinc aluminum strontium phosphosilicate, zinc phosphomolybdate, aluminum zinc phosphomolybdate, zinc strontium phosphostrontium, and zinc molybdate.

[0034] Furthermore, the pigments and fillers are selected from one or a combination of carbon black, iron oxide red, iron oxide yellow, chrome yellow, ultramarine, iron blue, titanium green, rutile titanium dioxide, kaolin, talc, mica powder, wollastonite powder, precipitated barium sulfate, silica fume, composite iron-titanium powder, ferrophosphate powder, heavy calcium carbonate, light calcium carbonate, calcite powder, dolomite powder, quartz powder, feldspar powder, polytetrafluoroethylene powder, mica iron oxide, non-floating aluminum powder, glass flakes, aluminum hydroxide, magnesium hydroxide, and zinc oxide. These pigments and fillers can improve the corrosion resistance and hardness of the paint film, increase its sealing properties, reduce roughness, improve its hiding power, prevent settling, and adjust the viscosity of the slurry.

[0035] Furthermore, the coating also includes additives, which can be selected from one or a combination of wetting and dispersing agents, defoamers, leveling agents, and thixotropic agents. In practical applications, the additives can be selected according to the needs.

[0036] Furthermore, the epoxy curing agent is selected from amine curing agents; it is preferably selected from curing agents with multifunctionality and network structure to increase the sealing of the paint film and improve corrosion resistance; it is preferably selected from combinations of curing agents with different curing rates to take into account the requirements of workability and pot life; it is particularly preferred to be selected from one or a combination of aliphatic amines, cycloaliphatic amines, phenolic amines, polyamides, and modified amines.

[0037] Furthermore, a fourth objective of this invention is to provide a method for preparing a highly sealed, environmentally friendly, and corrosion-resistant coating, which is also an objective of this invention.

[0038] Specifically, the method includes the following steps: Step 1: Disperse and mix the components including epoxy resin, reactive diluent, and optional additives; then gradually add the components including anti-settling agent, rust inhibitor, and pigments and fillers, and disperse and mix them to obtain component A; Step 2: Disperse and mix the components, including epoxy curing agent and optional curing accelerator, to obtain component B; Step 3: Mix component A and component B in the specified ratio to obtain the above-mentioned highly sealed environmentally friendly anti-corrosion coating.

[0039] More specifically, the method includes the following steps: Step 1: Disperse the components, including epoxy resin, additives, and reactive diluent, using a high-speed disperser at a stirring speed of 600–1000 r / min for approximately 10–30 min. Then, gradually add the components, including anti-settling agent, rust inhibitor, and pigments / fillers, adjusting the stirring speed to 800–2000 r / min and continuing to disperse for 30–60 min. Control the fineness to ≤40 μm, filter, and discharge to obtain component A. Step 2: Disperse and mix the components, including epoxy curing agent and curing accelerator, at high speed. Disperse for about 10 to 40 minutes at a stirring speed of 600 to 2000 r / min. Filter and discharge to obtain component B. Step 3: Mix component A and component B in the specified ratio to obtain the above-mentioned highly sealed environmentally friendly anti-corrosion coating.

[0040] Finally, the fifth objective of this invention is to provide the application of the highly sealed, environmentally friendly anti-corrosion coating, which is the third objective of this invention.

[0041] Specifically, the third objective of this invention is to provide a high-sealing, environmentally friendly anti-corrosion coating for use in equipment operating in high-humidity, high-salt, and high-ultraviolet radiation environments.

[0042] More specifically, the third objective of this invention, the application method of the highly sealed, environmentally friendly anti-corrosion coating, is as follows: Mix components A and B in the specified proportions. Depending on the application method, epoxy thinner may be used selectively, with the amount not exceeding 10% of the total paint volume. Apply by roller coating, brush coating, air spraying, or airless spraying.

[0043] Compared with the prior art, the beneficial effects of the present invention are as follows: (1) The bio-based epoxy resin used in this invention has multiple epoxy functionalities, which significantly improves the sealing properties of the resin system after curing, bringing excellent anti-corrosion properties to the coating, and is particularly suitable for harsh deep-sea environments and outdoor environments with severe corrosion.

[0044] (2) The high-sealing environmentally friendly anti-corrosion coating provided by the present invention has excellent anti-settling properties, anti-sagging properties, high adhesion, high single-coat film thickness, salt spray resistance, solvent resistance and other excellent properties. It can be used in construction, industry, petrochemical, shipbuilding and other fields. The single-coat film thickness can reach 500μm, which can reduce the number of construction times, shorten the construction cycle and realize rapid coating. The thickness can reach 2mm. It can be used with various topcoats such as polyurethane, fluorocarbon, and acrylic, and has a wide range of applications.

[0045] (3) The high-sealing environmentally friendly anti-corrosion coating of the present invention has low VOC and can be applied by roller coating, brush coating, air spraying, airless spraying and other methods. Attached Figure Description

[0046] Figure 1 The diagram shows the structure of the bio-based epoxy resins prepared in Examples 1-4 of this invention. Figure 2 This is a roadmap for the bio-based epoxy resins prepared in Examples 1-4 of the present invention. Detailed Implementation

[0047] The present invention will now be described in detail with reference to the accompanying drawings and embodiments. It should be noted that the following embodiments are only used to further illustrate the present invention and should not be construed as limiting the scope of protection of the present invention. Some non-essential improvements and adjustments made by those skilled in the art based on the content of the present invention are still within the scope of protection of the present invention.

[0048] Example 1 This embodiment illustrates the preparation of a highly sealing, environmentally friendly anti-corrosion coating, using the following raw materials and their weight proportions: First, the raw materials and quantities used in component A are as follows: 100 parts by weight of bio-based epoxy resin were prepared in-house. 40 parts by weight of bis(7-oxabicyclo[4.1.0]3-heptylmethyl) adipate, Shanghai Hanhong Technology; 20 parts by weight of ethylene glycol diglycidyl ether, Zhongshan Dixing Chemical Co., Ltd. Modified urea solution anti-settling agent RHEOBYK-410 1 part by weight BYK; Organic bentonite SD-11 parts by weight Elementis; Modified aluminum tripolyphosphate, 20 parts by weight, Xinsheng Chemical; Zinc phosphomolybdate, 20 parts by weight, Jiangsu Shenlong; Strontium zinc phosphosilicate SZP-39110 parts by weight HALOX; 10 parts by weight of wollastonite powder, Bai Ruixin Materials; 115 parts by weight of 1000 mesh talc powder from Haicheng Xufeng; 15 parts by weight of titanium dioxide from Ishihara, Japan; 5 parts by weight of Jiangxi Black Cat carbon black; 20 parts by weight of feldspar powder from Qianhao Minerals; 15 parts by weight of ultrafine mica powder, Haiyang powder; Wetting and dispersing agent Efka® FA 4663 AN4 parts by weight BASF; Defoamer Efka® SI 27222 parts by weight BASF; Leveling agent Efka® FL 3670 4 parts by weight BASF; Secondly, the raw materials and dosages used in component B are as follows: Epoxy curing agent LITE 3040: 100 parts by weight of Cardolite; Accelerator 29505 parts by weight Huntsman; The following describes the preparation of bio-based epoxy resins. For detailed structures and preparation routes, please refer to [link to documentation]. Figure 1 and Figure 2 : (1) At room temperature, 301 g (1 mol) of dobutamine was dispersed in 300 g of ethyl acetate at a high speed of 600 rd / min. (2) Under N2 protection and high-speed dispersion, the temperature was lowered to 0℃, and 124.3g (0.55mol) of L-lysine diisocyanate was added dropwise to (1), and the reaction was carried out for 1h; (3) Under N2 protection and high-speed dispersion, 971g (10.5mol) epichlorohydrin was added to (2), the temperature was raised to 60℃, and 420g (10.5mol) of NaOH aqueous solution (mass concentration 40%) was added dropwise. The reaction was carried out for 2h. (4) Under N2 protection and high-speed dispersion, the temperature was raised to 90℃ and the reaction continued for 4 hours, then cooled to room temperature; (5) Wash with water until neutral, remove solvent and unreacted monomer by vacuum distillation, add propylene glycol methyl ether acetate, adjust the solid content to 60%, and obtain a light yellow viscous liquid to obtain bio-based epoxy resin for later use.

[0049] The following is used to illustrate the preparation of highly sealing, environmentally friendly anti-corrosion coatings: Step 1, Component A: Disperse epoxy resin, additives, and reactive diluent using a high-speed disperser at a stirring speed of 1000 r / min for about 30 min; then gradually add anti-settling agent, rust inhibitor, and pigments / fillers, adjust the stirring speed to 1800 r / min, and continue dispersing for 30 min; control the fineness to ≤40μm, filter, discharge and package to obtain Component A; Step 2, Component B: The epoxy curing agent and curing accelerator, in the amounts described, are dispersed using a high-speed disperser at a stirring speed of 1800 r / min for about 10 min, filtered, discharged, and packaged to obtain Component B; Components A and B are used in a 6:1 ratio.

[0050] Example 2 This embodiment illustrates the preparation of a highly sealing, environmentally friendly anti-corrosion coating, using the following raw materials and their weight proportions: First, the raw materials and quantities used in component A are as follows: 100 parts by weight of bio-based epoxy resin were prepared in-house. 20 parts by weight of neopentyl glycol diglycidyl ether (Beijing Bailingwei); 20 parts by weight of 1,4-bis[(glycidoxy)methyl]cyclohexane, Tianjin Xins; Polyhydroxycarboxylic acid amide solution anti-settling agent RHEOBYK-4053 parts by weight BYK; Fumed silica HB-1505, parts by weight, Hubei Huifu; 10 parts by weight of zinc phosphate, Yinchen micro powder; Strontium phosphosilicate SW-11110 parts by weight HALOX; 10 parts by weight of aluminum tripolyphosphate, Weihai Tianchuang; 10 parts by weight of kaolin from Zhongshi Hengda; 90 parts by weight of 1250 mesh talc powder, Hongde colored sand; 70 parts by weight of mica powder from Hebei Kexu; 20 parts by weight of Yuejiang Titanium Dioxide; 10 parts by weight of iron oxide red from Hunan Sanhuan; Efka® PX 47801 parts by weight BASF as a wetting and dispersing agent; Defoamer Defom 68000.5 parts by weight Elementis; Leveling agent BYK-346 0.5 parts by weight BYK; Secondly, the raw materials and dosages used in component B are as follows: Epoxy curing agent Aradur 450 100 parts by weight Huntsman; The following describes how bio-based epoxy resins are prepared: (1) At room temperature, 301 g (1 mol) of dobutamine was dispersed in 300 g of ethyl acetate at a high speed of 800 rd / min. (2) Under N2 protection and high-speed dispersion, the temperature was lowered to 10℃, and 135.6g (0.6mol) of L-lysine diisocyanate was added dropwise to (1), and the reaction was carried out for 2h; (3) Under N2 protection and high-speed dispersion, 832.5g (9mol) epichlorohydrin was added to (2), the temperature was raised to 65℃, and 360g (9mol) of NaOH aqueous solution (mass concentration 40%) was added dropwise. The reaction was carried out for 1h. (4) Under N2 protection and high-speed dispersion, the temperature was raised to 80°C and the reaction continued for 6 hours, then cooled to room temperature; (5) Wash with water until neutral, remove solvent and unreacted monomer by vacuum distillation, add propylene glycol methyl ether acetate, adjust the solid content to 60%, and obtain a light yellow viscous liquid, which is the bio-based epoxy resin for later use.

[0051] The preparation process of the high-sealing environmentally friendly anti-corrosion coating in this embodiment is the same as that of the coating in Example 1, except that components A and B are used in a ratio of 7:1.

[0052] Example 3 This embodiment illustrates the preparation of a highly sealing, environmentally friendly anti-corrosion coating, using the following raw materials and their weight proportions: First, the raw materials and quantities used in component A are as follows: 50 parts by weight of bio-based epoxy resin were prepared in-house. BECKOPOX™ EP 11650 parts by weight, a new epoxy resin; 30 parts by weight of diglycidyl adipic acid (Shanghai Bangcheng); 20 parts by weight of diglycidyl cyclohexane-1,2-dicarboxylic acid ester, Hubei Zhenbo; Polyamide wax (EFKA RM 1463) 2 parts by weight BASF; Wax powder (Luwax AF29) 4 parts by weight BASF; Zinc aluminum molybdenum phosphate (HEUCOPHOS® ZAM PLUS) 15 parts by weight Heubach; HALOX® 70010 parts by weight of aluminum zinc phosphate; 10 parts by weight of modified aluminum tripolyphosphate, Xinsheng Chemical; 15 parts by weight of titanium dioxide from DuPont, USA; 50 parts by weight of 400 mesh ferric oxide from Anhui Sihuan; 10 parts by weight of Oersted silica powder; Light calcium carbonate, 80 parts by weight, Shandong Yuxin; 5 parts by weight of calcite powder, Zhenwei Chemical; Disponer 9833 parts by weight of Elementis (wetting and dispersing agent); Foamex defoamer N0.5 parts by weight TEGO; Leveling agent DC5 11.5 parts by weight DOW CORNING; Secondly, the raw materials and dosages used in component B are as follows: Epoxy curing agent JT-6015A 100 parts by weight, Shanghai Jingtian; Curing accelerator CUREZOL 2MZ-A2 (parts by weight, Shikoku Chemicals, Japan); The following is used to illustrate the preparation of bio-based epoxy resins: (1) At room temperature, 301 g (1 mol) of dobutamine was dispersed in 300 g of ethyl acetate at a high speed of 600 rd / min. (2) Under N2 protection and high-speed dispersion, the temperature was lowered to 5℃, and 131g (0.58mol) of L-lysine diisocyanate was added dropwise to (1), and the reaction was carried out for 2h; (3) Under N2 protection and high-speed dispersion, 925g (10mol) epichlorohydrin was added to (2), the temperature was raised to 60℃, and 400g (10mol) of NaOH aqueous solution (mass concentration 40%) was added dropwise. The reaction was carried out for 3h. (4) Under N2 protection and high-speed dispersion, the temperature was raised to 90℃ and the reaction continued for 5 hours, then cooled to room temperature; (5) Wash with water until neutral, remove solvent and unreacted monomer by vacuum distillation, add propylene glycol methyl ether acetate, adjust the solid content to 60%, and obtain a light yellow viscous liquid, i.e. bio-based epoxy resin.

[0053] The following is used to illustrate the preparation of highly sealing, environmentally friendly anti-corrosion coatings: Step 1, Component A: Disperse epoxy resin, additives, and reactive diluent using a high-speed disperser at a stirring speed of 800 r / min for about 20 min; then gradually add anti-settling agent, rust inhibitor, and pigments / fillers, adjust the stirring speed to 1600 r / min, and continue dispersing for 50 min; control the fineness to ≤40μm, filter, discharge, and package Component A; Step 2, Component B: The epoxy curing agent and curing accelerator, in the amounts described, are dispersed using a high-speed disperser at a stirring speed of 800 r / min for about 40 minutes, filtered, discharged, and packaged to obtain Component B; Components A and B are used in a 9:1 ratio.

[0054] Example 4 This embodiment illustrates the preparation of a highly sealing, environmentally friendly anti-corrosion coating, using the following raw materials and their weight proportions: First, the raw materials and quantities used in component A are as follows: Epoxy resin EPIKOTE 1001-X-75 30 parts by weight HEXION; 30 parts by weight of NPEL epoxy resin from South Asia; 40 parts by weight of bio-based epoxy resin were prepared in-house. 30 parts by weight of glycerol propoxy triglycidyl ether, Zhongshan Dixin; Sasolwax Spray 30-G: 1.5 parts by weight of Sasol; 2.5 parts by weight of fumed silica (Aerosil A200) from Evonik; 15 parts by weight of Heubach zinc molybdenum polyphosphate (HEUCOPHOS® ZAPP); Strontium zinc phosphosilicate HALOX® SZP-39115 parts by weight; Zinc strontium phosphate (JP-B808) 15 parts by weight, Shanghai Junjiang; 10 parts by weight of titanium dioxide from Saudi Arabia; 5 parts by weight of iron oxide yellow from Zhejiang Huayuan Pigment; Five parts by weight of kaolin from Yongfeng, Guangdong; 30 parts by weight of mica powder, Shijiazhuang Chenxing; 20 parts by weight of feldspar powder from Gree New Materials; 50 parts by weight of Japanese sheet glass flakes; Wetting and dispersing agent BYK-9076, 4 parts by weight BYK; Defoamer BYK-A5301 parts by weight BYK; Leveling agent Glide B 14842 parts by weight TEGO; Secondly, the raw materials and dosages used in component B are as follows: Epoxy curing agent PLR720 100 parts by weight, Changshu Naisu; Curing accelerator DMP-303 parts by weight (Kautschuk); The following is used to illustrate the preparation of bio-based epoxy resins: (1) At room temperature, 301 g (1 mol) of dobutamine was dispersed in 300 g of ethyl acetate at a high speed of 800 rd / min. (2) Under N2 protection and high-speed dispersion, the temperature was lowered to 5℃, and 131g (0.58mol) of L-lysine diisocyanate was added dropwise to (1), and the reaction was carried out for 2h; (3) Under N2 protection and high-speed dispersion, add 925g (10mol) epichlorohydrin to (2), heat to 70℃, add dropwise 400g (10mol) of NaOH aqueous solution (mass concentration 40%), and react for 3h; (4) Under N2 protection and high-speed dispersion, the temperature was raised to 90℃ and the reaction continued for 5 hours, then cooled to room temperature; (5) Wash with water until neutral, remove solvent and unreacted monomer by vacuum distillation, add propylene glycol methyl ether acetate, adjust the solid content to 60%, and obtain a light yellow viscous liquid, which is the bio-based epoxy resin for later use.

[0055] The following is used to illustrate the preparation of highly sealing, environmentally friendly anti-corrosion coatings: Step 1, Component A: Disperse epoxy resin, additives, and reactive diluent using a high-speed disperser at a stirring speed of 800 r / min for about 10 min; then gradually add anti-settling agent, rust inhibitor, and pigments and fillers, adjust the stirring speed to 1000 r / min, and continue dispersing for 60 min; control the fineness to ≤40μm, filter, discharge and package to obtain Component A; Step 2, Component B: The epoxy curing agent and curing accelerator, in the amounts described, are dispersed using a high-speed disperser at a stirring speed of 1000 r / min for about 20 min, filtered, discharged, and packaged to obtain Component B; Components A and B are used in a ratio of 10:1.

[0056] Comparative Example This comparative example illustrates the preparation of a highly sealed, environmentally friendly anti-corrosion coating. The preparation method and raw materials and weight parts used are the same as in Example 1, except that the epoxy resin used is EPIKOTE 1001-X-75.

[0057] The coatings prepared in the above embodiments and comparative examples were subjected to performance tests. The test standards and test results are shown in Table 1.

[0058] Table 1:

[0059] As shown in Table 1, the test results of Examples 1-4 above demonstrate that the high-sealing environmentally friendly anti-corrosion coating provided by this invention has excellent anti-settling properties, anti-sagging properties, high adhesion, and a single-coat film thickness of over 500μm, with a coating thickness of up to 2mm. Furthermore, the resulting coating exhibits excellent anti-corrosion properties, as well as excellent resistance to salt spray, cathodic disbondment, media resistance, and stirring temperature resistance. It can be used in construction, industry, petrochemical, and shipbuilding fields, and is especially suitable for deep-sea facilities and outdoor facilities.

[0060] The highly sealed, environmentally friendly anti-corrosion coating of the present invention preferably uses bio-based epoxy resin, which significantly improves the sealing properties of the resin system and brings excellent anti-corrosion properties to the coating.

[0061] The preferred embodiments of the present invention have been described in detail above; however, the present invention is not limited thereto. Within the scope of the inventive concept, various simple modifications can be made to the technical solutions of the present invention, including combinations of various technical features in any other suitable manner. These simple modifications and combinations should also be considered as the content disclosed in the present invention and are all within the protection scope of the present invention.

Claims

1. A bio-based epoxy resin, having a general structure of wherein, R1 is selected from one or a combination of a hydrogen atom, an alkyl group, and an alkylcarbonyl ester; R2 and R3 are each independently selected from one or a combination of a hydrogen atom and an alkyl group; a, b, and c are each independently selected from any integer from 1 to 20; h, f, and g are each independently selected from any integer from 1 to 3. 2.The bio-based epoxy resin of claim 1, wherein, when R1 is selected from an alkyl group, the alkyl group is selected from an alkyl group having 1-10 carbon atoms, preferably 2-8 carbon atoms; when R1 is selected from an alkylcarbonyl ester, the alkylcarbonyl ester has 1-10 carbon atoms, preferably 2-8 carbon atoms; and / or, when R2 and R3 are each independently selected from an alkyl group, the alkyl group has 1-8 carbon atoms, preferably 1-5 carbon atoms; and / or, a, b, and c are each independently selected from any integer from 2 to 10, preferably from 3 to 5; and / or, h, f, and g are each independently selected from any integer from 1 to 2. The bio-based epoxy resin is prepared by reacting a secondary amine derivative containing a phenolic hydroxyl group, a diisocyanate derivative, and an epoxy derivative. wherein, The secondary amine derivative containing a phenolic hydroxyl group has a general structure of wherein, R2 and R3 are each independently selected from one or a combination of a hydrogen atom and an alkyl group, the alkyl group being selected from an alkyl group having 1-8 carbon atoms, preferably 2-5 carbon atoms; b and c are each independently selected from any integer from 1 to 20, preferably from any integer from 2 to 10, more preferably from any integer from 3 to 5; 3. The method of producing a bio-based epoxy resin according to any one of claims 1-2, comprising the steps of: f and g are each independently selected from any integer from 1 to 3, preferably from any integer from 1 to 2; The diisocyanate derivative has a general structure of wherein, R1 is selected from one or a combination of a hydrogen atom, an alkyl group, and an alkylcarbonyl ester, the alkyl group and the alkylcarbonyl ester being selected from an alkyl group having 1-10 carbon atoms and an alkylcarbonyl ester having 1-10 carbon atoms, preferably from an alkyl group having 2-8 carbon atoms and an alkylcarbonyl ester having 2-8 carbon atoms; a is selected from any integer from 1 to 20, preferably from any integer from 2 to10, more preferably from any integer from 3 to 5; The epoxy derivative has a general structure of wherein, h is selected from any integer from 1 to 3, preferably from any integer from 1 to2; X is selected from halogen, preferably from chlorine. The preparation method comprises the following steps: Step one, dispersing the secondary amine derivative containing a phenolic hydroxyl group in a solvent, and adding the diisocyanate derivative at low temperature to obtain a first intermediate; Step two, adding the epoxy derivative and reacting under the action of a base to obtain the bio-based epoxy resin; Preferably, The molar ratio of the secondary amine derivative containing a phenolic hydroxyl group, the diisocyanate derivative, and the epoxy derivative is 1: (0.5-0.6): (9-12), preferably 1: (0.55-0.6): (9-10.5); and / or, 4. The method of producing a bio-based epoxy resin according to claim 3, characterized in that, In the step one, the low temperature is 0-20°C, and the reaction time is 1-2h; and / or, ​ ​ ​ ​ ​ In the step two, the reaction temperature is 50-90°C, and the reaction time is 1-6h; and / or, In the step two, the molar ratio of the epoxy derivative and the base is 1:(0.90-1.05); and / or, In the step two, the base is selected from sodium hydroxide.

5. A high-build, environmentally friendly anticorrosive coating, comprising an epoxy resin selected from the bio-based epoxy resin of any one of claims 1-2, or a combination of the bio-based epoxy resin of any one of claims 1-2 and one or more of a BPA-type epoxy resin, a polyurethane-modified epoxy resin, an acrylic-modified epoxy resin, a hydrogenated epoxy resin, a bio-based epoxy resin, wherein the bio-based epoxy resin has a mass that is at least 20%, preferably at least 30%, of the total mass of the epoxy resin.

6. The high-build, closed-rainbow, environmentally friendly anticorrosive coating of claim 5, wherein, comprising a component A and a component B, which are respectively formulated from raw materials comprising the following components, In the component A, by weight fraction: epoxy resin 100 parts by weight; active diluent 20-80 parts by weight, preferably 30-60 parts by weight; anti-settling agent 1-10 parts by weight, preferably 2-8 parts by weight; anti-rust filler 20-60 parts by weight, preferably 30-50 parts by weight; pigment 100-220 parts by weight, preferably 120-200 parts by weight; optional auxiliary agent 1-15 parts by weight, preferably 2-10 parts by weight; In the component B, by weight fraction: epoxy curing agent 100 parts by weight; optional curing accelerator 0-6 parts by weight, preferably 0-5 parts by weight; The weight ratio of the component A and the component B is (6-12):1, preferably (6-10):

1.

7. The high-build, environmentally friendly anticorrosive coating of claim 6, wherein, the active diluent is selected from one or a combination of aliphatic or cycloaliphatic di- or tri-functional glycidyl ethers or glycidyl esters; preferably one or a combination of triethylene glycol diglycidyl ether, ethylene glycol diglycidyl ether, diglycidyl ether, adipic acid diglycidyl ester, bis(7-oxabicyclo[4.1.0]3-heptamethyl) adipate, cyclohexane-1,2-dicarboxylic acid diglycidyl ester, glycerol triglycidyl ether, 2,2'-[(1-methylethylidene)bis(4,1-cyclohexyloxy methylene)]bisoxirane, 1,4-bis[(glycidyloxy)methyl]cyclohexane, 1,4-cyclohexane dimethanol diglycidyl ether, propylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, polyethylene glycol diglycidyl ether, glycerol diglycidyl ether, poly(propylene glycol) diglycidyl ether, glycerol propoxy triglycidyl ether, 1,2-cyclohexanediol diglycidyl ether, polyethylene glycol diglycidyl ether, 2,2-bis[(oxiranylmethyloxy)methyl]propane-1,3-diol, dipropylene glycol diglycidyl ether, trimethylol ethane triglycidyl ether, 3-[bis(glycidyloxymethyl)methoxy]-1,2-propanediol; and / or, The anti-settling agent is selected from one or a combination of organobentonite, attapulgite, lithium magnesium silicate, wax powder, polyamide wax, fumed silica, hydrogenated castor oil and its derivatives, modified polyurea solution, titanate coupling agent, polyhydroxycarboxylic acid amide solution, and montmorillonite; and / or, The rust-inhibiting filler is selected from one or a combination of zinc phosphate, modified zinc phosphate, composite zinc phosphate, aluminum tripolyphosphate, modified aluminum tripolyphosphate, calcium phosphate, zinc aluminum phosphate, zinc aluminum molybdenum phosphate, strontium aluminum polyphosphate, zinc molybdenum polyphosphate, calcium aluminum polyphosphate, calcium phosphosilicate, strontium phosphosilicate, barium phosphosilicate, zinc strontium phosphosilicate, calcium strontium phosphosilicate, calcium strontium phosphosilicate, zinc phosphomolybdate, aluminum zinc phosphomolybdate, zinc strontium phosphostrontium, and zinc molybdate; and / or, The pigments and fillers are selected from one or a combination of carbon black, iron oxide red, iron oxide yellow, chrome yellow, ultramarine, iron blue, titanium green, rutile titanium dioxide, kaolin, talc powder, mica powder, wollastonite powder, precipitated barium sulfate, silica fume, composite iron-titanium powder, ferrophosphate powder, heavy calcium carbonate, light calcium carbonate, calcite powder, dolomite powder, quartz powder, feldspar powder, polytetrafluoroethylene powder, mica iron oxide, non-floating aluminum powder, glass flakes, aluminum hydroxide, magnesium hydroxide, and zinc oxide; and / or, The epoxy curing agent is selected from amine curing agents; preferably from multifunctional curing agents with a network structure or combinations of curing agents with different curing rates; more preferably from one or a combination of aliphatic amines, cycloaliphatic amines, phenolic amines, polyamides, and modified amines.

8. A method for preparing a highly sealing, environmentally friendly anti-corrosion coating according to any one of claims 5-7, comprising the following steps: Step 1: Disperse and mix the components including epoxy resin, reactive diluent, and optional additives; then gradually add the components including anti-settling agent, rust inhibitor, and pigments and fillers, and disperse and mix them to obtain component A; Step 2: Disperse and mix the components, including epoxy curing agent and optional curing accelerator, to obtain component B; Step 3: Mix component A and component B in the specified ratio to obtain the highly sealed environmentally friendly anti-corrosion coating.

9. The method for preparing the highly sealed environmentally friendly anti-corrosion coating according to claim 8, characterized in that, In step one, the stirring speed is 600–2000 r / min, and the stirring time is 10–60 min; and / or, In step two, the stirring speed is 600–2000 r / min and the stirring time is 10–40 min.

10. The application of the highly sealed environmentally friendly anti-corrosion coating according to any one of claims 5-7, for coating equipment used in high humidity, high salt, and high ultraviolet radiation environments.

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