A pinoic acid modified epoxy resin, a preparation method thereof, and a polar applicable high-elastic low-temperature resistant anticorrosive coating, a preparation method and application thereof

Abstract

This invention discloses a pinic acid-modified epoxy resin and its preparation method, as well as a highly elastic, low-temperature resistant anti-corrosion coating suitable for polar environments, its preparation method, and its application. It relates to the field of anti-corrosion coating technology. The preparation method of the pinic acid-modified epoxy resin of this invention includes: preparing the pinic acid-modified epoxy resin by ring-opening esterification of raw materials including 1,3-bis(4'-glycidyl ether phenyl)adamantane, pinic acid, a catalyst, and a solvent. The highly elastic, low-temperature resistant anti-corrosion coating suitable for polar environments disclosed in this invention has advantages such as low-temperature crack resistance, good corrosion resistance, environmental resistance, high low-temperature adhesion, and good flexibility. Application methods include roller coating, brush coating, air spraying, and airless spraying, with a single-coat film thickness of up to 200 μm. It is particularly suitable for corrosion protection in polar environments, compatible with various intermediate and topcoats, has a wide range of applications, provides effective anti-corrosion protection, and has an effective film life of up to 20 years.

Description

Technical Field

[0001] This invention relates to the field of anti-corrosion coatings technology, and more specifically, to a pinic acid-modified epoxy resin and its preparation method, and a highly elastic, low-temperature resistant anti-corrosion coating suitable for polar regions and its preparation method and application. Background Technology

[0002] my country attaches great importance to polar exploration and has polar facilities such as research icebreakers, polar drilling platforms, and Antarctic research stations for polar scientific research and development, as well as marine observation equipment, polar helicopters, snowmobiles, and other scientific research equipment. The extreme cold marine environment is characterized by extreme low temperatures (below -80℃), high salt spray corrosion, strong wind and wave impact, and periodic ice loads.

[0003] Protective coatings for polar equipment face severe challenges in extreme low-temperature environments. Low temperatures cause coatings to become brittle and crack, while high salt spray accelerates electrochemical corrosion. Existing commercially available anti-corrosion coatings cannot meet the dual requirements of low-temperature resistance and corrosion resistance in extremely cold environments, and their corrosion protection performance still falls short of actual needs. Summary of the Invention

[0004] To address the problems existing in the prior art, this invention provides a pinic acid-modified epoxy resin and its preparation method, as well as a high-elasticity, low-temperature resistant anti-corrosion coating suitable for polar environments, its preparation method, and its application. The high-elasticity, low-temperature resistant anti-corrosion coating for polar environments disclosed in this invention possesses advantages such as low-temperature crack resistance, good corrosion resistance, environmental resistance, high low-temperature adhesion, and good flexibility. Application methods include roller coating, brush coating, air spraying, and airless spraying, with a single-coat film thickness reaching 200μm. It can be applied to various substrates such as steel, aluminum alloys, titanium alloys, fiber-reinforced composite materials, and wood, and is particularly suitable for corrosion protection in polar environments. It is compatible with various intermediate and topcoats, has a wide range of applications, provides effective anti-corrosion protection, and has a film lifespan of up to 20 years.

[0005] One of the objectives of this invention is to provide a pinic acid-modified epoxy resin.

[0006] The pinic acid-modified epoxy resin of the present invention has the following structural formula: .

[0007] A second objective of this invention is to provide a method for preparing pinic acid-modified epoxy resin as described in one objective of this invention.

[0008] The method for preparing pinic acid-modified epoxy resin according to the present invention includes: The pinic acid-modified epoxy resin is prepared by ring-opening esterification of raw materials including 1,3-bis(4'-glycidyl ether phenyl)adamantane, pinic acid, catalyst, and solvent; preferably, (1) A mixture was prepared by high-speed dispersion of 1,3-bis(4'-glycidyl ether phenyl)adamantane and pinic acid; (2) The catalyst is dispersed in a solvent to obtain a catalyst dispersion; (3) The catalyst dispersion is added dropwise to the mixture to carry out ring-opening esterification reaction to obtain the pinic acid modified epoxy resin.

[0009] Pinic acid brings low viscosity and colorfastness to modified epoxy resins; 1,3-bis(4'-glycidyl ether phenyl)adamantane can provide modified epoxy resins with cold resistance, elasticity, low-temperature flexibility, solvent resistance, strong adhesion, aging resistance, and chemical corrosion resistance; all raw materials used can be used in the pharmaceutical field and are environmentally friendly.

[0010] In a preferred embodiment of the present invention: The molar ratio of 1,3-bis(4'-glycidyl ether phenyl)adamantane to pinonic acid is (1.5~2.5):1, preferably (1.9~2.1):1; and / or, The molar ratio of the catalyst to 1,3-bis(4'-glycidyl ether phenyl)adamantane is (0.1~2.5):100, preferably (0.5~2):100; and / or, The concentration of the catalyst after dispersion in the solvent is 30-70 wt%, preferably 40-60 wt%.

[0011] In a preferred embodiment of the present invention: The catalyst is at least one of N,N-dimethylbenzylamine, N-methylethanolamine, and imidazoline; and / or, The solvent is a high-boiling-point solvent, preferably at least one of propylene glycol diacetate, ethylene glycol diacetate, divalent ester (DBE), and diethylene glycol butyl ether.

[0012] In a preferred embodiment of the present invention: In step (1), the high-speed dispersion rotation speed is 600~2000 r / min; and / or, In step (3), the dropping is carried out under a protective gas atmosphere, and / or the dropping temperature is 70~90℃; and / or, In step (3), the ring-opening esterification reaction is carried out under a protective gas atmosphere, and / or the reaction temperature is 110~160℃, preferably 120~150℃, and / or the reaction is stopped when the acid value of the reaction solution is lower than 2mgKOH / g.

[0013] The following solutions can be adopted: (1) 1,3-bis(4'-glycidyl ether phenyl)adamantane and pinic acid were mixed in proportion under high-speed dispersion at 600-2000 r / min to prepare a mixture; (2) The catalyst is dispersed in a solvent to obtain a catalyst dispersion; (3) Under a protective gas atmosphere and at 70-90ºC, the catalyst dispersion is added dropwise to the mixture in step (1); (4) Under a protective gas atmosphere, the temperature is raised to 110~160℃ and the reaction time is 1~4h. When the acid value of the reaction solution is lower than 2mgKOH / g, the reaction is stopped, and the solution is cooled to room temperature to obtain pinic acid modified epoxy resin.

[0014] The above reaction equation is as follows:

[0015] In a preferred embodiment of the present invention: When N,N-di(3-aminopropyl)ethylethylamine is selected as the curing agent, the network resin structure formed after curing can further improve the elasticity of the paint film, thereby enhancing low-temperature flexibility and improving the sealing properties of the coating, resulting in excellent corrosion resistance. The modified epoxy resin after curing can have the following molecular structure:

[0016] In the formula, n is any integer from 1 to 100.

[0017] The third objective of this invention is to provide a highly elastic, low-temperature resistant, and corrosion-resistant coating suitable for polar regions.

[0018] The polar-suitable, high-elasticity, low-temperature resistant anti-corrosion coating of this invention comprises component A and component B, wherein component A and component B are prepared from raw materials comprising the following components: Component A includes modified epoxy resin, reactive diluent, iron oxide red, non-floating aluminum powder, rust-preventive pigment, pigments and fillers, additives, and epoxy diluent; Component B includes an epoxy curing agent and optionally a curing accelerator; The modified epoxy resin includes at least one of the following: pinic acid modified epoxy resin as described in one of the objectives of this invention, or pinic acid modified epoxy resin prepared by the method described in another objective of this invention, and optionally bisphenol A type epoxy resin (BPA type epoxy resin), phenolic epoxy resin, aliphatic epoxy resin, alicyclic epoxy resin, and polyurethane modified epoxy resin. Component A, by weight parts: 100 parts by weight of modified epoxy resin; 5-20 parts by weight of reactive diluent; 5-20 parts by weight of iron oxide red; 5-20 parts by weight of non-floating aluminum powder; 10-25 parts by weight of anti-rust pigment; Pigments and fillers: 100-180 parts by weight; 2-20 parts by weight of auxiliary agent; 25-50 parts by weight of epoxy diluent; The components B, by weight, are: 100 parts by weight of epoxy curing agent; Curing accelerator: 0-10 parts by weight; The weight ratio of component A to component B is (6-12):1.

[0019] In a preferred embodiment of the present invention: Component A, by weight parts: 100 parts by weight of modified epoxy resin; 6-15 parts by weight of reactive diluent; 6-10 parts by weight of iron oxide red; 6-15 parts by weight of non-floating aluminum powder; 12-20 parts by weight of anti-rust pigment; Pigments and fillers: 110-160 parts by weight; 6-18 parts by weight of additives; 30-45 parts by weight of epoxy diluent; Component B, by weight: 100 parts by weight of epoxy curing agent; Curing accelerator: 0-5 parts by weight; The weight ratio of component A to component B is (7-11):1.

[0020] In a preferred embodiment of the present invention: The active dilution can be a commonly used active dilution in the art; and / or, The rust-preventive pigment is at least one of zinc phosphate, modified zinc phosphate, composite zinc phosphate, aluminum tripolyphosphate, modified aluminum tripolyphosphate, calcium phosphate, aluminum strontium polyphosphate, zinc aluminum phosphate, calcium phosphosilicate, strontium phosphosilicate, barium phosphosilicate, zinc strontium phosphosilicate, zinc phosphomolybdate, aluminum zinc phosphomolybdate, zinc strontium phosphostrontium, zinc molybdate, and calcium borosilicate; and / or, The pigments and fillers are at least one of the following: rutile titanium dioxide, kaolin, talc, mica powder, wollastonite powder, precipitated barium sulfate, silica fume, composite iron-titanium powder, ferrophosphorus powder, heavy calcium carbonate, light calcium carbonate, calcite powder, feldspar powder, polytetrafluoroethylene powder, aluminum hydroxide, magnesium hydroxide, zinc oxide, and lithium magnesium silicate. They have the functions of improving the corrosion resistance and hardness of the paint film, increasing the sealing properties of the paint film, reducing roughness, improving the hiding power of the paint film, preventing sedimentation, and adjusting the viscosity of the slurry; and / or, The additives mentioned are commonly used additives in the art, such as wetting and dispersing agents, thickeners, leveling agents, defoamers, etc., which can be added by those skilled in the art according to the actual situation; and / or, The epoxy diluent is a mixture of a low-boiling-point solvent and a high-boiling-point solvent; preferably, the weight ratio of the low-boiling-point solvent to the high-boiling-point solvent is (2-4):1; and / or, the low-boiling-point solvent is at least one selected from xylene, butanol, butyl acetate, and propylene glycol methyl ether acetate; and / or, the high-boiling-point solvent is at least one selected from propylene glycol diacetate, ethylene glycol diacetate, divalent ester (DBE), and diethylene glycol butyl ether; and / or, The epoxy curing agent is an amine-based curing agent, preferably N,N-di(3-aminopropyl)ethylethylamine, which has trifunctionality. The cured resin system can form a network structure, which can increase the sealing properties of the paint film and improve its corrosion resistance; and / or, The curing accelerator is a small molecule polyamine.

[0021] The fourth objective of this invention is to provide a method for preparing a high-elasticity, low-temperature resistant, and corrosion-resistant coating suitable for polar applications, as described in the third objective of this invention.

[0022] The method for preparing the polar-suitable, high-elasticity, low-temperature resistant anti-corrosion coating of the present invention comprises: Component A is prepared by mixing the components in the specified weight proportions; Component B is prepared by mixing the components in the specified weight proportions; and the anti-corrosion coating is prepared by mixing the components A and B in the specified weight ratio.

[0023] The specific preparation method is as follows: Component A: The modified epoxy resin, additives, reactive diluent, and 40-60 wt% epoxy diluent are dispersed using a high-speed disperser at a stirring speed of 600-1000 rpm for approximately 10-30 minutes. Then, iron oxide red, rust-preventive pigments, and fillers are gradually added, and the stirring speed is adjusted to 800-2000 rpm, continuing dispersion for 30-60 minutes. Finally, non-floating aluminum powder and the remaining epoxy diluent are added, and the stirring speed is adjusted to 200-600 rpm, dispersing for 30-60 minutes. The fineness is controlled to ≤40. m m, filtration, discharge packaging; Component B: Disperse according to the dosage described above using a high-speed disperser at a stirring speed of 600-2000 r / min for approximately 10-40 min, then filter, discharge, and package. When in use, the anti-corrosion coating is prepared by mixing component A and component B in the specified proportion.

[0024] The fifth objective of this invention is to provide an application of a polar-suitable, high-elasticity, low-temperature resistant anti-corrosion coating as described in the third objective of this invention, or a polar-suitable, high-elasticity, low-temperature resistant anti-corrosion coating prepared by the method provided in the fourth objective of this invention, in the field of corrosion protection.

[0025] The specific usage method is as follows: During application, mix components A and B in the specified proportions. Depending on the application method, epoxy thinner may be used selectively, but the amount should not exceed 10% of the total paint volume. Application methods include roller coating, brush coating, air spraying, and airless spraying. The maximum single-coat film thickness can reach 200 mm. m m.

[0026] The present invention has the following beneficial effects: (1) The pinic acid modified epoxy resin of the present invention has low viscosity and can be used to prepare high-solids, low-viscosity, high-elasticity, low-temperature resistant anti-corrosion coatings suitable for polar applications; the four-membered alicyclic structure and adamantane structure contained therein give the resin high sealing properties, elasticity, colorfastness, and aging resistance, thereby significantly improving the anti-corrosion properties of high-elasticity, low-temperature resistant anti-corrosion coatings suitable for polar applications; the long-chain structure gives the resin good flexibility, improves the low-temperature flexibility of high-elasticity, low-temperature resistant anti-corrosion coatings suitable for polar applications, and avoids cracking of the coating when thickly applied at extreme low temperatures; the network resin structure formed after curing can improve the sealing properties of the coating and further enhance the anti-corrosion and chemical corrosion resistance of the coating.

[0027] (2) The high-elasticity, low-temperature resistant anti-corrosion coating suitable for polar applications of the present invention has the advantages of low-temperature crack resistance, thick coating flexibility, low VOC, good corrosion resistance, environmental resistance, high low-temperature adhesion, and good flexibility. Application methods include roller coating, brush coating, air spraying, and airless spraying. A single coat thickness can reach 200 mm. m m. It can be applied to various substrates such as steel, aluminum alloy, titanium alloy, fiber-reinforced composite materials, and wood. It is especially suitable for corrosion protection in polar environments. It can be used with various intermediate paints and topcoats. It has a wide range of applications, provides effective anti-corrosion protection, and the effective life of the paint film can reach up to 20 years.

[0028] (3) The coating of the present invention is not only simple to process and easy to industrialize, but also has good stability.

[0029] In this article, the term "and / or" is merely a description of the relationship between related objects, indicating that there can be three relationships, such as A and / or B. Specifically, it can mean that A and B can be included at the same time, A can exist alone, or B can exist alone, and any of the above three situations can be met. Detailed Implementation

[0030] The present invention will now be described in detail with reference to specific 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.

[0031]

Example 1

[0032] Preparation of high-elasticity, low-temperature resistant, and corrosion-resistant coatings suitable for polar regions: The raw materials and dosages used in component A are as follows: Pinic acid modified epoxy resin 100 parts by weight Reactive diluent LGE 15 parts by weight, Guodu Chemical; Iron oxide red S1306, parts by weight, Shanghai Yipin; 15 parts by weight of non-floating aluminum powder ALPASTE® from Toyo Aluminum Co., Ltd. Zinc Aluminum Phosphate (ZPA) 4 parts by weight, Heubach; Sapproxene aluminum polyphosphate (SAPP) 8 parts by weight Heubach; 15 parts by weight of titanium dioxide from Chemours; Talc powder 1250 mesh 50 parts by weight Jiangsu Dongli; Light calcium carbonate, 30 parts by weight, dolomite powder; 15 parts by weight of ferrophosphorus powder from Hangzhou Kainuoen; 50 parts by weight of mica powder, one of the three treasures of Guangdong; Wetting and dispersing agent BYK-21523 parts by weight BYK; Thickener Crayvallac® MT1 parts by weight ARKEMA; Leveling agent Glide 4501 parts by weight TEGO; Defoamer EFKA SI27221 parts by weight BASF; 10 parts by weight of xylene, ExxonMobil; Butanol, 10 parts by weight, Tiande Chemical Co., Ltd. 10 parts by weight of propylene glycol diacetate (DOW); The raw materials and dosages used in component B are as follows: Epoxy curing agent LITE 3040: 100 parts by weight of Cardolite; Accelerator 960 - 15 parts by weight Huntsman; The weight ratio of component A to component B is 7:1.

[0033] The preparation method is as follows: Component A: The pinic acid-modified epoxy resin, additives, reactive diluent, and 40% epoxy diluent are dispersed using a high-speed disperser at a stirring speed of 800–1000 rpm for approximately 10 minutes. Then, iron oxide red, rust-preventive pigments, and fillers are gradually added, and the stirring speed is adjusted to 1800–2000 rpm, continuing dispersion for 30 minutes. Next, non-floating aluminum powder and the remaining epoxy diluent are added, and the stirring speed is adjusted to 200–400 rpm, dispersing for 30 minutes. The fineness is controlled to ≤40 μm, then filtered, discharged, and packaged. Component B: Disperse all raw materials using a high-speed disperser at a stirring speed of 1800-2000 r / min for about 10 minutes, then filter, discharge and package. Component A and Component B are mixed in a weight ratio of 7:1.

[0034]

Example 2

[0035] Preparation of high-elasticity, low-temperature resistant, and corrosion-resistant coatings suitable for polar regions: The raw materials and dosages used in component A are as follows: Pinic acid modified epoxy resin 100 parts by weight Reactive diluent EX-1216 parts by weight, Nagase; Ultrafine iron oxide red (Red 130M, 10 parts by weight) BAYFERROX; Non-floating aluminum powder STAPA HP Z6 parts by weight ECKART; Modified aluminum tripolyphosphate, 12 parts by weight, Xinsheng Chemical; 4 parts by weight of zinc phosphomolybdate from Jiangsu Shenlong; Strontium zinc phosphosilicate SZP-3914 parts by weight HALOX; 15 parts by weight of titanium dioxide from Zhongnuan Titanium Dioxide; 15 parts by weight of kaolin from Yongfeng, Guangdong; 10 parts by weight of silicon micropowder from Anhui Gerui; Precipitated barium sulfate, 50 parts by weight, from Yuejiang titanium dioxide; 20 parts by weight of feldspar powder from Anhui Gerui; Wetting and dispersing agent XL 6577, 6 parts by weight of Allnex; Thickener MP 1003 parts by weight BYK; 35706 parts by weight of leveling agent AFCONA; Defoamer Defom 2700 3 parts by weight Elementis; 36 parts by weight of propylene glycol methyl ether acetate; 9 parts by weight of divalent ester DBE Invista; The raw materials and dosages used in component B are as follows: 100 parts by weight of N,N-di(3-aminopropyl)ethylethylamine (Wuhan Xinweiye) The weight ratio of component A to component B is 11:1.

[0036] The preparation method is as follows: Component A: The pinic acid-modified epoxy resin, additives, reactive diluent, and 60% epoxy diluent component are dispersed using a high-speed disperser at a stirring speed of 600-800 rpm for approximately 30 minutes. Then, iron oxide red, rust-preventive pigments, and fillers are gradually added, and the stirring speed is adjusted to 800-1000 rpm, continuing dispersion for another 60 minutes. Next, non-floating aluminum powder and the remaining epoxy diluent are added, and the stirring speed is adjusted to 200-400 rpm, dispersing for another 60 minutes. The fineness is controlled to be ≤40 μm, then filtered, discharged, and packaged. Component B: Directly packaged and used; Component A and Component B are mixed in a weight ratio of 11:1.

[0037]

Example 3

[0038] Preparation of high-elasticity, low-temperature resistant, and corrosion-resistant coatings suitable for polar regions: The raw materials and dosages used in component A are as follows: Modified epoxy resin NPEL 40 parts by weight, South Asia; Pinyl acid modified epoxy resin 60 parts by weight Reactive diluent EPOX 23609 parts by weight SACHEM; Iron oxide red L2915D 9 parts by weight BASF; Non-floating aluminum powder FD-512H9 parts by weight AsahiKASEI; Zinc strontium phosphate JP-B8085 parts by weight, Shanghai Junjiang; 5 parts by weight of zinc molybdate from Jiangsu Shenlong; Calcium phosphate 430 JM5 parts by weight HALOX; 20 parts by weight of titanium dioxide from Anhui Annada; 80 parts by weight of talc powder from Guangdong Yongfeng 80 parts by weight of calcite powder from Lingyun, Guangxi Wetting and dispersing agent FX 90865 parts by weight Elementis; Thickener CRAYVALLAC SLT 2 parts by weight Arkema; Leveling agent LAMBDA 3 parts by weight Allnex; Defoamer Efka PB 2720 2 parts by weight BASF; Butanol, 10 parts by weight, Tiande Chemical Co., Ltd. 10 parts by weight of butyl acetate, Qianxin Chemical Co., Ltd. 10 parts by weight of propylene glycol methyl ether acetate, Jiangsu Hualun; 10 parts by weight of diethylene glycol butyl ether, Jiangsu Yida; The raw materials and dosages used in component B are as follows: Epoxy curing agent PLR720 100 parts by weight, Changshu Naisu; The weight ratio of component A to component B is 9:1.

[0039] The preparation method is as follows: Component A: Mix the modified epoxy resin, additives, reactive diluent, and 50% epoxy diluent using a high-speed disperser at a stirring speed of 700-900 rpm for approximately 20 minutes. Then, gradually add iron oxide red, rust-preventive pigments, and fillers, adjusting the stirring speed to 1000-1200 rpm and continuing to disperse for 45 minutes. Add non-floating aluminum powder and the remaining epoxy diluent, adjusting the stirring speed to 300-500 rpm and dispersing for 30 minutes. Control the fineness to ≤40 μm, filter, and package the product. Component B: Directly packaged and used; Component A and Component B are mixed in a weight ratio of 9:1.

[0040]

Example 4

[0041] The preparation method is as follows: Component A: The pinic acid-modified epoxy resin, additives, reactive diluent, and 50% epoxy diluent component are dispersed using a high-speed disperser at a stirring speed of 600–800 rpm for approximately 20 minutes. Then, iron oxide red, rust-preventive pigments, and fillers are gradually added, and the stirring speed is adjusted to 1200–1500 rpm, continuing dispersion for 40 minutes. Next, non-floating aluminum powder and the remaining epoxy diluent are added, and the stirring speed is adjusted to 200–400 rpm, dispersing for 30 minutes. The fineness is controlled to ≤40 μm, then filtered, discharged, and packaged. Component B: Disperse the entire amount using a high-speed disperser at a stirring speed of 600-800 r / min for about 40 minutes, then filter, discharge and package. Component A and Component B are mixed in a weight ratio of 10:1.

[0042] Comparative Example 1 Preparation of anti-corrosion coatings: The raw materials and dosages used in component A are as follows: Epoxy resin 8301-B85 / 9007-33250 parts by weight, Changxing Chemical; BECKOPOX™ EP 11650 parts by weight, a new epoxy resin; Reactive diluent LGE 15 parts by weight, Guodu Chemical; Iron oxide red S1306, parts by weight, Shanghai Yipin; 15 parts by weight of non-floating aluminum powder ALPASTE® from Toyo Aluminum Co., Ltd. Zinc Aluminum Phosphate (ZPA) 4 parts by weight, Heubach; Sapproxene aluminum polyphosphate (SAPP) 8 parts by weight Heubach; 15 parts by weight of titanium dioxide from Chemours; Talc powder 1250 mesh 50 parts by weight Jiangsu Dongli; Light calcium carbonate, 30 parts by weight, dolomite powder; 15 parts by weight of ferrophosphorus powder from Hangzhou Kainuoen; 50 parts by weight of mica powder, one of the three treasures of Guangdong; Wetting and dispersing agent BYK-21523 parts by weight BYK; Thickener Crayvallac® MT1 parts by weight ARKEMA; Leveling agent Glide 4501 parts by weight TEGO; Defoamer EFKA SI27221 parts by weight BASF; 10 parts by weight of xylene, ExxonMobil; Butanol, 10 parts by weight, Tiande Chemical Co., Ltd. 10 parts by weight of propylene glycol diacetate (DOW); The raw materials and dosages used in component B are as follows: Epoxy curing agent LITE 3040: 100 parts by weight of Cardolite; Accelerator 960 - 15 parts by weight Huntsman; The weight ratio of component A to component B is 7:1.

[0043] The anti-corrosion coatings prepared in the above embodiments and comparative examples were subjected to performance tests, and the test results are shown in Table 1 below.

[0044] Table 1

[0045] The test results of Examples 1-4 above show that the high-elasticity, low-temperature resistant anti-corrosion coating suitable for polar environments prepared in the embodiments of the present invention has advantages such as low-temperature crack resistance, low-temperature corrosion resistance, low-temperature flexibility, high low-temperature adhesion, and environmental resistance. It can be used in industries such as construction, petrochemicals, bridges, ships, and steel structures, and is especially suitable for corrosion protection in polar environments. The preferred pinic acid-modified epoxy resin system of the high-elasticity, low-temperature resistant anti-corrosion coating suitable for polar environments of the present invention is superior to that in the prior art in terms of low-temperature flexibility, resistance to alternating temperatures, low-temperature performance, salt spray resistance, and resistance to cathodic disbondment. Furthermore, the present invention optimizes and adjusts the structure of the pinic acid-modified epoxy resin, thereby significantly improving the corrosion resistance of the high-elasticity, low-temperature resistant anti-corrosion coating suitable for polar environments. The long-chain structure gives the resin good flexibility, improves the low-temperature flexibility of the high-elasticity, low-temperature resistant anti-corrosion coating suitable for polar environments, and avoids cracking of the coating when used in thick coatings at extreme low temperatures, resulting in high corrosion resistance. The high-solids content system is green, environmentally friendly, and pollution-free during construction.

Claims

1. A pinic acid-modified epoxy resin, characterized in that... The structural formula of the pinic acid-modified epoxy resin is: 。 2. A method for preparing the pinic acid-modified epoxy resin as described in claim 1, characterized in that... The method includes: The pinic acid-modified epoxy resin is prepared by ring-opening esterification of raw materials including 1,3-bis(4'-glycidyl ether phenyl)adamantane, pinic acid, catalyst, and solvent; preferably, (1) A mixture was prepared by high-speed dispersion of 1,3-bis(4'-glycidyl ether phenyl)adamantane and pinic acid; (2) The catalyst is dispersed in a solvent to obtain a catalyst dispersion; (3) The catalyst dispersion is added dropwise to the mixture to carry out ring-opening esterification reaction to obtain the pinic acid modified epoxy resin.

3. The method according to claim 2, characterized in that: The molar ratio of 1,3-bis(4'-glycidyl ether phenyl)adamantane to pinonic acid is (1.5~2.5):1, preferably (1.9~2.1):1; and / or, The molar ratio of the catalyst to 1,3-bis(4'-glycidyl ether phenyl)adamantane is (0.1~2.5):100, preferably (0.5~2):100; and / or, The concentration of the catalyst after dispersion in the solvent is 30-70 wt%, preferably 40-60 wt%.

4. The method according to claim 2, characterized in that: The catalyst is at least one of N,N-dimethylbenzylamine, N-methylethanolamine, and imidazoline; and / or, The solvent is a high-boiling-point solvent, preferably at least one of propylene glycol diacetate, ethylene glycol diacetate, divalent ester, and diethylene glycol butyl ether.

5. The method according to claim 2, characterized in that: In step (1), the high-speed dispersion rotation speed is 600~2000 r / min; and / or, In step (3), the dropping is carried out under a protective gas atmosphere, and / or the dropping temperature is 70~90℃; and / or, In step (3), the ring-opening esterification reaction is carried out under a protective gas atmosphere, and / or the reaction temperature is 110~160℃, preferably 120~150℃, and / or the reaction is stopped when the acid value of the reaction solution is lower than 2mgKOH / g.

6. A high-elasticity, low-temperature resistant, anti-corrosion coating suitable for polar regions, characterized in that... The anti-corrosion coating comprises component A and component B, which are prepared from raw materials including the following components: Component A includes modified epoxy resin, reactive diluent, iron oxide red, non-floating aluminum powder, rust-preventive pigment, pigments and fillers, additives, and epoxy diluent; Component B includes an epoxy curing agent and optionally a curing accelerator; The modified epoxy resin includes the pinic acid modified epoxy resin as described in claim 1 or the pinic acid modified epoxy resin prepared by the method as described in any one of claims 1-5, and optionally at least one of bisphenol A type epoxy resin, phenolic epoxy resin, aliphatic epoxy resin, alicyclic epoxy resin, and polyurethane modified epoxy resin. Component A, by weight parts: 100 parts by weight of modified epoxy resin; 5-20 parts by weight of reactive diluent; 5-20 parts by weight of iron oxide red; 5-20 parts by weight of non-floating aluminum powder; 10-25 parts by weight of anti-rust pigment; Pigments and fillers: 100-180 parts by weight; 2-20 parts by weight of auxiliary agent; 25-50 parts by weight of epoxy diluent; Component B, by weight: 100 parts by weight of epoxy curing agent; Curing accelerator: 0-10 parts by weight; The weight ratio of component A to component B is (6-12):

1.

7. The anti-corrosion coating according to claim 6, characterized in that: Component A, by weight parts: 100 parts by weight of modified epoxy resin; 6-15 parts by weight of reactive diluent; 6-10 parts by weight of iron oxide red; 6-15 parts by weight of non-floating aluminum powder; 12-20 parts by weight of anti-rust pigment; Pigments and fillers: 110-160 parts by weight; 6-18 parts by weight of additives; 30-45 parts by weight of epoxy diluent; Component B, by weight: 100 parts by weight of epoxy curing agent; Curing accelerator: 0-5 parts by weight; The weight ratio of component A to component B is (7-11):

1.

8. The anti-corrosion coating according to claim 6 or 7, characterized in that: The rust-preventive pigment is at least one of zinc phosphate, modified zinc phosphate, composite zinc phosphate, aluminum tripolyphosphate, modified aluminum tripolyphosphate, calcium phosphate, aluminum strontium polyphosphate, zinc aluminum phosphate, calcium phosphosilicate, strontium phosphosilicate, barium phosphosilicate, zinc strontium phosphosilicate, zinc phosphomolybdate, aluminum zinc phosphomolybdate, zinc strontium phosphostrontium, zinc molybdate, and calcium borosilicate; and / or, The pigments and fillers are at least one selected from rutile titanium dioxide, kaolin, talc, mica powder, wollastonite powder, precipitated barium sulfate, silica fume, composite iron-titanium powder, ferrophosphorus powder, heavy calcium carbonate, light calcium carbonate, calcite powder, feldspar powder, polytetrafluoroethylene powder, aluminum hydroxide, magnesium hydroxide, zinc oxide, and lithium magnesium silicate; and / or, The epoxy diluent is a mixture of a low-boiling-point solvent and a high-boiling-point solvent; preferably, the weight ratio of the low-boiling-point solvent to the high-boiling-point solvent is (2-4):1; and / or, the low-boiling-point solvent is at least one selected from xylene, butanol, butyl acetate, and propylene glycol methyl ether acetate; and / or, the high-boiling-point solvent is at least one selected from propylene glycol diacetate, ethylene glycol diacetate, divalent ester, and diethylene glycol butyl ether; and / or, The epoxy curing agent is an amine curing agent, preferably N,N-di(3-aminopropyl)ethylethylamine; and / or, The curing accelerator is a small molecule polyamine.

9. A method for preparing a high-elasticity, low-temperature resistant, anti-corrosion coating suitable for polar applications as described in any one of claims 6-8, characterized in that... The method includes: Component A is prepared by mixing the components in the specified weight proportions; Component B is prepared by mixing the components in the specified weight proportions; and the anti-corrosion coating is prepared by mixing the components A and B in the specified weight ratio.

10. The application of a polar-suitable high-elasticity low-temperature resistant anti-corrosion coating as described in any one of claims 6-8, or a polar-suitable high-elasticity low-temperature resistant anti-corrosion coating prepared by the method described in claim 9, in the field of corrosion protection.

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