A cerium ion coordination terpyridyl group antiseptic and flame-retardant bifunctional filler, a preparation method and application thereof

Abstract

The application discloses a cerium ion coordination terpyridyl group anti-corrosion and flame-retardant dual-functional filler, a preparation method and application thereof, and has a structural formula. The application has the dual-functional characteristics of anti-corrosion and flame-retardation, uses a siloxane skeleton structure as a connecting agent to improve the toughness of EP; DOPO contains phosphorus elements, and a phosphorus compound can be decomposed at high temperature to generate phosphorus oxide, and these oxides can form a protective layer in a flame to reduce the interaction between oxygen and combustible materials, and the combustion reaction is slowed down or inhibited; pyridine can adsorb metal ions in a corrosive environment to play an anti-corrosion role; meanwhile, N atoms on the pyridine ring can generate N2 in the combustion process, which can dilute the oxygen concentration in the gas and play an important role in the intumescent flame-retardant process; Ce 3+ is coordinated with pyridine to form a coordination compound, a dense adsorption film is formed on the surface of a matrix, and corrosion protection is provided; meanwhile, it can combine a plurality of small molecule monomers to form a long chain chelate, and the performance of the filler is further improved.

Description

Technical Field

[0001] This invention belongs to the field of anti-corrosion and flame-retardant coating technology, specifically relating to a cerium ion-coordinated terpyridine-based anti-corrosion and flame-retardant bifunctional filler, its preparation method, and its application. Background Technology

[0002] With the rapid development of industries such as marine transportation, marine engineering, new energy development, and new chemical materials, the performance requirements for coatings on offshore equipment, such as offshore oil platforms and near-shore steel structures, are becoming increasingly stringent. These structures not only require coatings with excellent corrosion resistance but also stringent fire resistance requirements. However, existing steel structure coatings often only possess a single function, such as fire retardant or anti-corrosion coatings. While some coatings on the market offer both fire retardancy and corrosion resistance, they typically involve complex application processes, are costly, and may peel off due to poor compatibility, thus affecting the protective effect. Therefore, developing a dual-function coating that combines corrosion resistance and fire resistance, achieving an integrated design for both corrosion protection and protection, can solve the problems of cumbersome processes associated with mixing fire retardant and anti-corrosion coatings.

[0003] In the field of corrosion protection, epoxy resin is one of the most widely used substrate coating materials, favored for its excellent substrate adhesion and chemical stability. However, epoxy resin also has some problems during use. For example, during curing, defects such as bubbles and cracks may form inside the epoxy matrix, which can compromise the protective properties of the coating. Epoxy resin is also relatively brittle and prone to cracking; its functions are relatively limited, and it is flammable. These problems restrict the application scenarios of epoxy resin. Therefore, developing multifunctional coating materials is particularly important. Summary of the Invention

[0004] The purpose of this invention is to overcome the defects of the prior art and provide a cerium ion-coordinated terpyridine-based anti-corrosion and flame-retardant dual-function filler.

[0005] Another objective of this invention is to provide a method for preparing the above-mentioned cerium ion-coordinated terpyridine-based anti-corrosion and flame-retardant bifunctional filler.

[0006] Another object of the present invention is to provide the application of the above-mentioned cerium ion coordinated terpyridine-based anti-corrosion and flame-retardant bifunctional filler.

[0007] The technical solution of the present invention is as follows:

[0008] A cerium ion-coordinated terpyridine-based anti-corrosion and flame-retardant bifunctional filler, the structural formula of which is as follows:

[0009]

[0010] The preparation method of the above-mentioned cerium ion-coordinated terpyridine-based corrosion-resistant and flame-retardant bifunctional filler includes: mixing functionalized terpyridine, cerium nitrate hexahydrate, and anhydrous ethanol, and reacting them at 58-62℃, wherein the structural formula of the functionalized terpyridine is as follows:

[0011] In a preferred embodiment of the present invention, the functionalized terpyridine is prepared by reacting TPY, DP-P, and DOPO in anhydrous ethanol, wherein the structural formula of TPY is as follows: The structural formula of DP-P is The structural formula of DOPO is

[0012] A further preferred embodiment of the TPY synthesis route is as follows:

[0013]

[0014] More preferably, the synthesis route of the DP-P is as follows:

[0015]

[0016] The above-mentioned cerium ion-coordinated terpyridine-based anti-corrosion and flame-retardant bifunctional filler is used in the preparation of anti-corrosion and flame-retardant organic resin coating compositions.

[0017] In a preferred embodiment of the present invention, the organic resin substrate in the anti-corrosion and flame-retardant organic resin coating composition is selected from epoxy resin, polyurethane and polyester resin, silicone resin, silicone / acrylic modified epoxy resin and silicone modified phenolic epoxy vinyl ester resin.

[0018] A corrosion-resistant and flame-retardant organic resin coating composition having the above-mentioned cerium ion-coordinated terpyridine-based corrosion-resistant and flame-retardant dual-function filler.

[0019] In a preferred embodiment of the present invention, the organic resin substrate is selected from epoxy resin, polyurethane and polyester resin, silicone resin, silicone / acrylic modified epoxy resin and silicone modified phenolic epoxy vinyl ester resin.

[0020] Further preferred ingredients include leveling agents, defoamers, dispersants, and antisettling agents.

[0021] The beneficial effects of this invention are:

[0022] 1. The siloxane skeleton structure in this invention is used as a binder and also improves the toughness of EP.

[0023] 2. The DOPO phosphorus-containing compound in this invention will eventually produce polyphosphoric acid during combustion, which will catalyze the formation of carbon and achieve excellent flame retardant properties.

[0024] 3. The pyridine in this invention can adsorb metal ions in a corrosive environment, thus playing a role in corrosion prevention. At the same time, the N atom on the pyridine ring can generate N2 during combustion, which can dilute the concentration of oxygen in the gas and play an important role in the expansion flame retardant process.

[0025] 4. Ce in this invention 3+ Ce coordinates with pyridine to form a coordination compound. 3+ It can also form a dense oxide layer on the substrate surface, providing corrosion protection. Simultaneously, it can combine various small-molecule monomers to form long-chain chelates, further improving the filler's performance.

[0026] 5. This invention develops a composite ternary expansion system, which comprehensively applies flame retardant-smoke suppression synergistic flame retardant technology such as phosphorus, nitrogen and inorganic flame retardants, as well as halogen-free flame retardant technology, to improve the product's fire resistance limit and further endow the product with environmental protection significance. Attached Figure Description

[0027] Figure 1 This is a synthesis route diagram for the cerium ion-coordinated terpyridine-based anti-corrosion and flame-retardant bifunctional filler of the present invention.

[0028] Figure 2 The infrared spectra of the raw materials TPY, DP-P, DOPO and the products CN and CE in this embodiment of the invention are shown.

[0029] Figure 3 Optical photographs of steel plates subjected to 60 days of salt spray chamber testing for the coating samples obtained in Examples 1 to 6 of this invention: (a) EP; (b) CN-0.25%; (c) CN-0.5%; (d) CN-1%; (e) CE-0.25%; (f) CE-0.5%; (g) CE-1%.

[0030] Figure 4 The results of the coating electrochemical impedance spectroscopy test on the coating samples obtained in Examples 1 to 6 of the present invention are shown in the figure.

[0031] Figure 5 The coating cone calorimetry residual carbon diagrams of the coating samples obtained in Example 7 of the present invention include (a) EP and (b) CE-5%.

[0032] Figure 6 The figures shown are vertical combustion test results of the coating samples obtained in Example 7 of the present invention, including (a) EP and (b) CE-5%. Detailed Implementation

[0033] The technical solution of the present invention will be further explained and described below with reference to specific embodiments and accompanying drawings.

[0034] Example 1

[0035] (1) 3.17 g of p-nitrobenzaldehyde was placed in a round-bottom flask containing 170 mL of methanol. Then, 5 g of 2-acetylpyridine and 160 mL of ammonia were added to the flask. 15 mL of 15 wt% KOH solution was then added dropwise and the mixture was stirred for 72 h. The mixture was then filtered, and the residue was washed with water and methanol until the filtrate was colorless and transparent. The residue was then dried to obtain the intermediate product, nitrophenyltripyridine. 1 g of nitrophenyltripyridine and 0.2 g of palladium on carbon were placed in a three-necked flask, and 200 mL of ethanol was added as the reaction solvent. The mixture was heated to 85 °C and reacted for 48 h. During heating, 15 mL of hydrazine hydrate was added as a reducing agent. After the reaction was complete, the filtrate was filtered, precipitated in brine, and then filtered, washed, and dried sequentially to obtain the final product TPY (infrared spectrum as shown in the image). Figure 2 (As shown).

[0036] (2) Dissolve 0.1 mol of p-hydroxybenzaldehyde in 100 mL of THF, add 0.11 mol of triethylamine, and transfer the mixture to a three-necked round-bottom flask with a nitrogen inlet and a condenser tube. Add 0.05 mol of diphenyldichlorosilane dropwise to the flask in an ice bath, and continue the reaction at 40 °C for 4 h to synthesize the product DP-P (infrared spectrum as shown). Figure 2 (as shown), and purified by filtration and rotary evaporation to remove triethylamine hydrochloride and THF.

[0037] (3) Dissolve 1g TPY in 150mL of anhydrous ethanol in a three-necked round-bottom flask and stir well. Then dissolve 0.65g DP-P in anhydrous ethanol and add it to the three-necked round-bottom flask. Heat to 50℃ and react for 6h. Then add 0.67g DOPO (infrared spectrum as shown) Figure 2 The solution (as shown) was dissolved in anhydrous ethanol and added to the three-necked round-bottom flask; the temperature was then raised to 70°C and maintained for 24 hours; an orange transparent liquid was obtained by filtration, and the liquid was poured into brine, precipitating a pale yellow precipitate. The precipitate was filtered and dried to obtain the crude product; the crude product was purified with chloroform and water, and finally dried under vacuum at 80°C to obtain CN (infrared spectrum as shown). Figure 2 As shown, the synthesis route is as follows Figure 1 (As shown).

[0038] (4) Weigh 0.0875g CN (0.25% of epoxy resin solid content), and ultrasonically disperse it evenly in 2mL of a mixed solvent of xylene and n-butanol with a volume ratio of 4:1. Then add it to 56g of dissolved epoxy resin and stir and disperse it for 30min at a high speed of 2000r / min or higher. During stirring, add appropriate amounts of additives: 0.24g each of BYK-333 leveling agent, BYK-066N defoamer, BYK-P104 dispersant and BYK-410 antisettling agent, and continue stirring for 30min. Then add 11.6g of curing agent polyamide 8200, continue stirring for 15min, and then centrifuge at high speed to eliminate the bubbles generated by stirring.

[0039] (5) The material obtained in step (4) is coated onto the steel plate using a wire bar coater to prepare a coating sample (CN-0.25%).

[0040] (6) After curing, the coating sample obtained in step (5) is subjected to performance testing.

[0041] The above performance tests include salt spray chamber testing, coating electrochemical impedance testing, and mechanical performance testing.

[0042] Test results are as follows Figure 3 , Figure 4 As shown in Table 1.

[0043] Example 2

[0044] The process is basically the same as in Example 1, except that in step (4), 0.175g of CN (0.5% of the epoxy resin solid content) is weighed, and the resulting coating sample is denoted as CN-0.5%. The test results are as follows... Figure 3 , Figure 4 As shown in Table 1.

[0045] Example 3

[0046] The process is basically the same as in Example 1, except that in step (4), 0.35g of CN (1% of the epoxy resin solid content) is weighed, and the resulting coating sample is denoted as CN-1%. The test results are as follows... Figure 3 , Figure 4 As shown in Table 1.

[0047] Example 4

[0048] Steps (1) to (3) are the same as in Example 1.

[0049] (4) Weigh equal amounts of CN and Ce(NO3)3·6H2O, react them in ethanol solvent at 60℃ for 6 h, and filter to obtain the filtrate. Add the filtrate to brine to precipitate an orange solid precipitate, and then filter, wash and dry successively to obtain the final multifunctional coordination compound CN-Ce.3+ (CE) (Infrared spectrum such as) Figure 2 As shown, the synthesis route is as follows Figure 1 (As shown).

[0050] (5) Weigh 0.0875g CE (0.25% of the solid content of epoxy resin), and ultrasonically disperse it evenly in a mixed solvent of xylene and n-butanol. Then add it to 56g of dissolved epoxy resin and stir and disperse it for 30min at a high speed of 2000r / min or higher. During stirring, add appropriate amounts of additives: 0.24g each of BYK-333 leveling agent, BYK-066N defoamer, BYK-P104 dispersant and BYK-410 antisettling agent, and continue stirring for 30min. Then add 11.6g of curing agent polyamide 8200, continue stirring for 15min, and then centrifuge at high speed to eliminate the bubbles generated by stirring.

[0051] (6) The material obtained in step (5) is coated onto the steel plate using a wire bar coater to prepare a coating sample (CE-0.25%).

[0052] (7) After curing, the coating sample obtained in step (6) is subjected to performance testing.

[0053] The above performance tests include salt spray chamber testing, coating electrochemical impedance testing, and mechanical performance testing.

[0054] Test results are as follows Figure 3 , Figure 4 As shown in Table 1.

[0055] Example 5

[0056] The process is basically the same as in Example 4, except that in step (5), 0.175g of CE (0.5% of the epoxy resin solid content) is weighed, and the resulting coating sample is denoted as CE-0.5%. The test results are as follows... Figure 3 , Figure 4 As shown in Table 1.

[0057] Example 6

[0058] The process is basically the same as in Example 4, except that in step (5), 0.35g of CE (1% of the epoxy resin solid content) is weighed, and the resulting coating sample is denoted as CE-1%. The test results are as follows... Figure 3 , Figure 4 As shown in Table 1.

[0059] Example 7

[0060] The process is basically the same as in Example 4, except that in step (5), 1.75g ​​of CE (5% of the epoxy resin solid content) is weighed, and the resulting coating sample is denoted as CE-5%. The coating sample of this example was subjected to cone calorimetry, vertical combustion, and mechanical property tests. The test results are as follows: Figure 5 , Figure 6 As shown in Table 1.

[0061] Table 1 Mechanical properties of epoxy resin modified with cerium ion-coordinated terpyridyl functional fillers

[0062]

[0063]

[0064] The above description is merely a preferred embodiment of the present invention, and therefore should not be construed as limiting the scope of the present invention. All equivalent changes and modifications made in accordance with the scope of the patent and the contents of the specification should still fall within the scope of the present invention.

Claims

1. A cerium ion-coordinated terpyridine-based anti-corrosion and flame-retardant dual-function filler, characterized in that: Its structural formula is 。 2. The preparation method of the cerium ion-coordinated terpyridine-based anti-corrosion and flame-retardant bifunctional filler according to claim 1, characterized in that: include: The functionalized terpyridine was prepared by reacting a mixture of functionalized terpyridine, cerium nitrate hexahydrate, and anhydrous ethanol at 58-62°C. The structural formula of the functionalized terpyridine is as follows:

3. The preparation method according to claim 2, characterized in that: The functionalized terpyridine was prepared by reacting TPY, DP-P, and DOPO in anhydrous ethanol, wherein the structural formula of TPY is as follows: The structural formula of DP-P is The structural formula of DOPO is 4. The preparation method according to claim 3, characterized in that: The synthetic route for TPY is as follows:

5. The preparation method according to claim 3, characterized in that: The synthesis route of DP-P is as follows:

6. The application of the cerium ion-coordinated terpyridyl anticorrosive and flame-retardant bifunctional filler according to claim 1 in the preparation of anticorrosive and flame-retardant organic resin coating compositions.

7. The application as described in claim 6, characterized in that: The organic resin substrate in the anti-corrosion and flame-retardant organic resin coating composition is selected from epoxy resin, polyurethane and polyester resin, silicone resin, silicone / acrylic modified epoxy resin and silicone modified phenolic epoxy vinyl ester resin.

8. A corrosion-resistant and flame-retardant organic resin coating composition, characterized in that: It has the cerium ion coordinated terpyridine-based anti-corrosion and flame retardant dual-function filler as described in claim 1.

9. The anti-corrosion and flame-retardant organic resin coating composition as described in claim 8, characterized in that: Its organic resin base material is selected from epoxy resin, polyurethane and polyester resin, silicone resin, silicone / acrylic modified epoxy resin and silicone modified phenolic epoxy vinyl ester resin.

10. The anti-corrosion and flame-retardant organic resin coating composition as described in claim 9, characterized in that: It also includes leveling agents, defoamers, dispersants, and antisettling agents.

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