ADDITIVE WITH SYNERGY, SELF-REPAIRING AND ANTI-CORROSION, AND APPLICATION THEREOF

Abstract

The disclosure relates to the technical field of coating anti-corrosion, in particular to an additive with synergy, self-repairing, anti-corrosion and its application. The additive includes hydrotalcite containing exchangeable anions and zeolite containing exchangeable cations. Compared with the prior art, the present disclosure has both cation and anion exchange performance. When the corrosive electrolyte enters the coating film, it is in contact with the corrosion-resistant additive, and the corrosive ions (such as chloride ions or sodium ions) are adsorbed during the process of penetrating into the coating, and the corresponding anti-corrosion anions and cations are released, precipitated in the coating to close the gaps of the coating, or transferred to the metal substrate to form a protective layer, thereby acting as a barrier to protect the substrate and enhance the adhesion of the coating. Its anti-rust effect is obvious, and it can replace the anti-rust pigment containing lead or chromium.

Claims

1. An additive with synergy, self-repairing and anti-corrosion, comprising hydrotalcite containing exchangeable anions and zeolite containing exchangeable cations wherein mass parts of the hydrotalcite is 10 to 80, and mass parts of the zeolite is 20 to 90, wherein the hydrotalcite contains or more of the following exchangeable anions between layers: carbonate, molybdate, vanadate, pyrovanadate, metavanadate, phosphate, phosphite, pyrophosphate, metaphosphate, tripolyphosphate, metaborate, chromate, and dichromate; wherein the zeolite contains one or more of the following exchangeable cations in its pores: trivalent aluminum ion, divalent zinc ion, divalent calcium ion, divalent barium ion, divalent manganese ion, trivalent iron ion, trivalent iron ion, valance chromium ion, divalent strontium ion and rare earth element ion; wherein the hydrotalcite is a modified hydrotalcite containing exchangeable anions prepared by an ion exchange method, wherein the zeolite is a modified zeolite containing exchangeable cations prepared by an ion exchange method.

2. (canceled)

3. (canceled)

4. (canceled)

5. The additive with synergy, self-repairing and anti-corrosion according to claim 1, wherein mass parts of the hydrotalcite is 30-60, and mass parts of the zeolite is 40-70.

6. (canceled)

7. (canceled)

8. An application of the additive with synergy, self-repairing and anti-corrosion of any one of claims 1-2 in preparation of anti-corrosive coatings.

9. The application according to claim 3, wherein an anti-corrosion mechanism is to absorb and exchange corrosive substances in the environment to form water-insoluble deposits, and the deposits can automatically fill and repair the gaps in the coating to prevent further penetration of corrosive substances.

10. A coating containing an additive with synergy, self-repairing and anti-corrosion according to any one of claims 1-2.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

[0037] FIG. 1 is the test result of the first example according to the present disclosure.

DETAILED DESCRIPTION OF EMBODIMENTS

[0038] The present disclosure will be further described below in combination with the accompanying drawings.

[0039] The specific embodiment is only an explanation of the present disclosure, and is not a limitation to the present disclosure. Any changes made by those skilled in the art after reading the specification of the present disclosure will be protected by the patent law as long as they fall within the scope of the claims.

Example 1

[0040] An additive with synergy, self-repairing and anti-corrosion, may be composed of 5A zeolite and phosphoric acid modified hydrotalcite. The details are as follows:

[0041] 1, 100 g of hydrotalcite may be added to 2000 g of water, and then stirred and dispersed at 75° C. for 1 hour; 75.26 g of trisodium phosphate that is 1.8 times the ion exchange capacity of the hydrotalcite may be added and continue the reaction for 1 hour. After the reaction is over, the powder may be centrifuged and dried;

[0042] 2, the 5A zeolite and the modified hydrotalcite may be physically blended at a molar ratio of 1:1 after exchange, to obtain an anti-corrosion additive.

Example 2

[0043] An additive with synergy, self-repairing and anti-corrosion, may be composed of zinc-modified clinoptilolite and molybdic acid-modified hydrotalcite. The details are as follows:

[0044] 1, 100 g of clinoptilolite powder may be added to 2000 g of water, and then stirred and dispersed at 75° C. for 1 hour; 30.96 g of zinc sulfate that is 1.8 times the ion exchange capacity of clinoptilolite may be added and continue the reaction for 1 hour. After the reaction is over, the powder may be centrifuged and dried;

[0045] 2, 100 g of hydrotalcite may be added to 2000 g of water, and then stirred and dispersed at 75° C. for 1 hour; 61.17 g of sodium molybdate that is 1.8 times the ion exchange capacity of the hydrotalcite may be added and continue the reaction for 1 hour. After the reaction is over, the powder may be centrifuged and dried;

[0046] 3, the modified clinoptilolite and hydrotalcite may be physically blended at a molar ratio of 1:1 after exchange, to obtain an anti-corrosion additive.

Example 3

[0047] An additive with synergy, self-repairing and anti-corrosion, may be composed of bismuth modified mordenite and vanadic acid modified hydrotalcite. The details are as follows:

[0048] 1, 100 g of mordenite powder may be added to 2000 g of water, and then stirred and dispersed at 75° C. for 1 hour; 52.9 g of bismuth nitrate that is 1.8 times the ion exchange capacity of clinoptilolite may be added and continue the reaction for 1 hour. After the reaction is over, the powder may be centrifuged and dried;

[0049] 2, 100 g of hydrotalcite may be added to 2000 g of water, and then stirred and dispersed at 75° C. for 1 hour; 36.4 g of sodium vanadate that is 1.8 times the ion exchange capacity of the hydrotalcite may be added and continue the reaction for 1 hour. After the reaction is over, the powder may be centrifuged and dried;

[0050] 3, the modified mordenite and the hydrotalcite may be physically blended at a molar ratio of 1:1 after exchange, to obtain an anti-corrosion additive.

Example 4

[0051] An additive with synergy, self-repairing and anti-corrosion, may be composed of aluminum modified clinoptilolite and phosphorous acid modified hydrotalcite. The details are as follows:

[0052] 1, 100 g of clinoptilolite powder may be added to 2000 g of water, and then stirred and dispersed at 75° C. for 1 hour; 43.7 g of aluminum sulfate that is 1.8 times the ion exchange capacity of clinoptilolite may be added and continue the reaction for 1 hour. After the reaction is over, the powder may be centrifuged and dried;

[0053] 2, 100 g of hydrotalcite may be added to 2000 g of water, and then stirred and dispersed at 75° C. for 1 hour; 64.2 g of sodium phosphite that is 1.8 times the ion exchange capacity of the hydrotalcite may be added and continue the reaction for 1 hour. After the reaction is over, the powder may be centrifuged and dried;

[0054] 3, the modified clinoptilolite and hydrotalcite may be physically blended at a molar ratio of 1:1 after exchange, to obtain an anti-corrosion additive.

Example 5

[0055] An additive with synergy, self-repairing and anti-corrosion, may be composed of cerium modified mordenite and citric acid modified hydrotalcite. The details are as follows:

[0056] 1, 100 g of mordenite powder may be added to 2000 g of water, and then stirred and dispersed at 75° C. for 1 hour; 58.1 g of cerium nitrate that is 1.8 times the ion exchange capacity of clinoptilolite may be added and continue the reaction for 1 hour. After the reaction is over, the powder may be centrifuged and dried;

[0057] 2, 100 g of hydrotalcite may be added to 2000 g of water, and then stirred and dispersed at 75° C. for 1 hour; 38.8 g of sodium citrate that is 1.8 times the ion exchange capacity of the hydrotalcite may be added and continue the reaction for 1 hour. After the reaction is over, the powder may be centrifuged and dried;

[0058] 3, the modified mordenite and the hydrotalcite may be physically blended at a molar ratio of 1:1 after exchange, to obtain an anti-corrosion additive.

Example 6

[0059] An additive with synergy, self-repairing and anti-corrosion, may be composed of aluminum modified clinoptilolite and tripolyphosphoric acid modified hydrotalcite. The details are as follows:

[0060] 1, 100 g of clinoptilolite powder may be added to 2000 g of water, and then stirred and dispersed at 75° C. for 1 hour; 43.7 g of aluminum sulfate that is 1.8 times the ion exchange capacity of clinoptilolite may be added and continue the reaction for 1 hour. After the reaction is over, the powder may be centrifuged and dried;

[0061] 2, 100 g of hydrotalcite may be added to 2000 g of water, and then stirred and dispersed at 75° C. for 1 hour; 43.7 g of sodium tripolyphosphate that is 1.8 times the ion exchange capacity of the hydrotalcite may be added and continue the reaction for 1 hour. After the reaction is over, the powder may be centrifuged and dried;

[0062] 3, the modified clinoptilolite and hydrotalcite may be physically blended at a molar ratio of 1:1 after exchange, to obtain an anti-corrosion additive.

Example 7

[0063] An additive with synergy, self-repairing and anti-corrosion, may be composed of zinc modified clinoptilolite and phosphoric acid modified hydrotalcite. The details are as follows:

[0064] 1, 100 g of clinoptilolite powder may be added to 2000 g of water, and then stirred and dispersed at 75° C. for 1 hour; 31.0 g zinc sulfate that is 1.8 times the ion exchange capacity of clinoptilolite may be added and continue the reaction for 1 hour. After the reaction is over, the powder may be centrifuged and dried;

[0065] 2, 100 g of hydrotalcite may be added to 2000 g of water, and then stirred and dispersed at 75° C. for 1 hour; 75.26 g of trisodium phosphate that is 1.8 times the ion exchange capacity of the hydrotalcite may be added and continue the reaction for 1 hour. After the reaction is over, the powder may be centrifuged and dried;

[0066] 3, the modified clinoptilolite and hydrotalcite may be physically blended at a molar ratio of 1:1 after exchange, to obtain an anti-corrosion additive.

Example 8

[0067] An additive with synergy, self-repairing and anti-corrosion, may be composed of lanthanum modified X-type zeolite and citric acid modified hydrotalcite. The details are as follows:

[0068] 1, 100 g of clinoptilolite powder may be added to 2000 g of water, and then stirred and dispersed at 75° C. for 1 hour; 110 g lanthanum nitrate that is 1.8 times the ion exchange capacity of clinoptilolite may be added and continue the reaction for 1 hour. After the reaction is over, the powder may be centrifuged and dried;

[0069] 2, 100 g of hydrotalcite may be added to 2000 g of water, and then stirred and dispersed at 75° C. for 1 hour; 58.2 g of sodium citrate that is 1.8 times the ion exchange capacity of the hydrotalcite may be added and continue the reaction for 1 hour. After the reaction is over, the powder may be centrifuged and dried;

[0070] 3, the modified X-type zeolite and the hydrotalcite may be physically blended at a molar ratio of 1:1 after exchange, to obtain an anti-corrosion additive.

Example 9

[0071] An additive with synergy, self-repairing and anti-corrosion, may be composed of hydrophobically modified 5A zeolite and phosphoric acid modified hydrotalcite. The details are as follows:

[0072] 1, 100 g of 5A zeolite powder may be added to 2000 g of water, and then stirred and dispersed at 75° C. for 1 hour; 3% octyltriethoxysilane powder may be added for hydrophobic modification and continue the reaction for 1 hour. After the reaction is over, the powder may be centrifuged and dried;

[0073] 2, 100 g of hydrotalcite may be added to 2000 g of water, and then stirred and dispersed at 75° C. for 1 hour; 75.26 g of trisodium phosphate that is 1.8 times the ion exchange capacity of the hydrotalcite may be added and continue the reaction for 1 hour. After the reaction is over, the powder may be centrifuged and dried;

[0074] 3, the modified 5A zeolite and the hydrotalcite may be physically blended at a molar ratio of 1:1 after exchange, to obtain an anti-corrosion additive.

[0075] The additive with synergy, self-repairing and anti-corrosion can be used in combination with anti-corrosion pigments and coloring pigments. It may be added before the high-speed dispersion and grinding stage of the coating. The addition amount may be 1%˜10% of the total coating formula. The commonly used addition amount may be 2%˜6%. The corrosion resistance evaluation method adopts ISO 4628, and the rust is divided into six levels, namely Ri0: rust area=0; Ri1: rust area≤0.05%; Ri2: rust area≤50.5%; Ri3: rust area≤1%, Ri4: rust area≤8%, Ri5: rust area is 40-50%. There are six levels of foaming, namely 0: no foaming; 1: fewer foaming; 2: more visible foaming with a particle size of less than 0.5 mm; 3: more foaming with a smaller particle size 0.5-5 mm; 4: foaming particle size greater than 5 mm; 5: severe foaming.

Application Example 1: The Additive with Synergy, Self-Repairing and Anti-Corrosion Applied to Water-Based Alkyd Resin Coatings

[0076]

TABLE-US-00002 Raw Material {circle around (1)} {circle around (2)} {circle around (3)} Water 14.8 14.8 14.8 K9N Fungicide 0.2 0.2 0.2 HYDROPALAT 34 Dispersant 1.0 1.0 1.0 HYDROPALAT 3037 Wetting 0.2 0.2 0.2 Agent FOMASTER-NXZ Defoamer 0.5 0.5 0.5 bayferrox 225 Iron Oxide Red 10 10 10 800 mesh Talcum Powder 12 12 12 800 mesh Barium Sulfate 8 10 8 Anti-corrosion Additive 2.0 Not 2.0 (Exam- added (Shieldex ple1) AC5) BP-188 Bentonite 0.4 0.4 0.4 Alcophor 827 Organic Corrosion 1.0 1.0 1.0 Inhibitor Uradil AZ3530 Alkyd Resin 43 43 43 ADDITOL VXW4940N Drier 0.7 0.7 0.7 Halox Flash-X 150 Anti-flash Rust 1.0 1.0 1.0 Agent EFKA3035 Leveling Agent 0.3 0.3 0.3 ACRYSOLTM RM-8W Thickener 0.4 0.4 0.4 Water 4.5 4.5 4.5 100 100 100 Rust Level Ri0 Ri2 Ril Foaming level 0 2 1

[0077] Specific operation: the 8 kinds of raw material, such as water, dispersant, defoamer, wetting agent, iron red, barium sulfate, talc, corrosion inhibitor and bentonite, may be pre-dispersed uniformly, and then alkyd resin, drier, leveling agent, anti-flash rust agent and thickener may be added to it, and dispersed again, they may be adjusted to the proper viscosity with water.

[0078] The board may be painted and sprayed according to the test formula given above, and placed at room temperature for 7 days, baked at 80° C. for 1 hour, and then put in a salt spray box for 500 hours. The test results are shown in FIG. 1. FIG. 1 is the anti-corrosion effect of the additive with synergy, self-repairing and anti-corrosion in the water-based alkyd paint ({circle around (1)} represents adding the anti-corrosion additive of the present disclosure; {circle around (2)} represents not adding the anti-corrosion additive; {circle around (3)} represents competitive anti-corrosion additive). The competitive anti-corrosion additive uses calcium ion exchange silica gel Shieldex AC5. The results show that the treatment of the present disclosure significantly improves the anti-corrosive effect of the water-based alkyd paint.

Application Example 2: The Additive with Synergy, Self-Repairing and Anti-Corrosion Applied in Waterborne Epoxy Primers

[0079]

TABLE-US-00003 Raw Material {circle around (1)} {circle around (2)} {circle around (3)} {circle around (4)} Water 12.6 12.6 12.6 12.6 K9N Fungicide 0.2 0.2 0.2 0.2 HYDROPALAT 34 1.0 1.0 1.0 1.0 Dispersant HYDROPALAT 3037 0.2 0.2 0.2 0.2 Wetting Agent FOMASTER-NXZ 0.5 0.5 0.5 0.5 Defoanner Lanninox F Mica Iron 14 14 14 14 Oxide 800 mesh Talcum 9 9 9 9 Powder Anti-Corrosion 10 10 10 10 Additive (Exam- (Exam- (HALOX391 (L203E ple2) ple3) zinc strontium phosphate) chromate) SMP-HV3 Bentonite 0.4 0.4 0.4 0.4 EPIKOTET ™ 50 50 50 50 6520-WH-53A Epoxy Resin Halox Flash-X 150 1.0 1.0 1.0 1.0 Anti-flash Rust Agent EFKA3035 leveling 0.3 0.3 0.3 0.3 agent ACRYSOLTM 0.8 0.8 0.8 0.8 RM-8W Thickener 100 100 100 100 EPIKURE 6870- 20 20 20 20 W-53 Curing Agent Rust Level Ri0 Ri0 Ri2 Ri0 Foaming Level 0 1 1 0

[0080] Specific operation: water, dispersant, defoamer, wetting agent, titanium dioxide, barium sulfate, talcum powder, and corrosion inhibitor, may be pre-dispersed uniformly, and then epoxy resin may be added to it, and dispersed again; anti-flash rust agent and leveling agent may be added, and uniformly dispersed and prepared.

[0081] The board may be painted and sprayed according to the test formula given above, with 20% modified alicyclic amine epoxy curing agent added, and placed at room temperature for 7 days, baked at 80° C. for 1 hour, and then put in a salt spray box for 800 hours. The test results show that the treatment of the present disclosure significantly improves the anti-corrosive effect of the water-based epoxy paint.

Application Example 3: The Additive with Synergy, Self-Repairing and Anti-Corrosion Applied in Solvent-Based Epoxy Primers

[0082] Specifically, the anti-corrosion epoxy primer may be formulated according to the following formula.

TABLE-US-00004 Raw Material {circle around (1)} {circle around (2)} {circle around (3)} {circle around (4)} E-51 Epoxy Resin 40 40 40 40 EFKA5220 Dispersant 0.5 0.5 0.5 0.5 EFKA2020 Defoanner 0.5 0.5 0.5 0.5 R-902 Rutile Titanium 13.5 13.5 13.5 13.5 Dioxide 800 mesh Barium Sulfate 12 12 12 12 800 mesh Talcum 10 10 10 10 Powder BP-127 Organic 0.5 0.5 0.5 0.5 Bentonite Anti-corrosion Additive 8.5 8.5 8.5 8.5 (Exam- (Exam- (K-white (243-XF ple 4) ple 5) 80 zinc aluminum chromate) phosphate) Halox 650 Organic 1.5 1.5 1.5 1.5 Anti-corrosion Agent Xylene 6.4 6.4 6.4 6.4 N-butanol 6.4 6.4 6.4 6.4 EFKA3772 Leveling 0.2 0.2 0.2 0.2 Agent 100 100 100 100 NX-2018 Phenalkannine 30 30 30 30 Curing Agent Rust Level Ri0 Ri0 Ri2 Ri0 Foaming Level 0 0 1 0

[0083] Specific operation: the materials in the above formula may be mixed and dispersed uniformly to prepare the additive.

[0084] The board may be painted and sprayed according to the test formula given above, placed at room temperature for 7 days, and then put in the salt spray box for 1000 hours. The results show that the treatment of the present disclosure makes the anti-corrosion effect of the epoxy primer significantly improved.

Application Example 4: The Additive with Synergy, Self-Repairing and Anti-Corrosion Applied in Water-Based Acrylic Coatings

[0085] Specifically, the anti-corrosive waterborne acrylic paint may be formulated according to the following formula.

TABLE-US-00005 Raw Material {circle around (1)} {circle around (2)} {circle around (3)} {circle around (4)} Water 13 13 13 13 K9N Fungicide 0.2 0.2 0.2 0.2 HYDROPALAT 34 1.0 1.0 1.0 1.0 Dispersant FOMASTER-NXZ 0.5 0.5 0.5 0.5 Defoanner HYDROPALAT 3037 0.2 0.2 0.2 0.2 Wetting Agent BP-188B Bentonite 0.3 0.3 0.3 0.3 Propylene Glycol 3.3 3.3 3.3 3.3 Texanol 0.7 0.7 0.7 0.7 bayferrox 225 Iron 10 10 10 10 Oxide Red 800 mesh Mica 4.3 4.3 4.3 4.3 800 mesh Talcum 10 10 10 10 Powder Anti-Corrosion 5 5 5 5 (Exam- (Exam- (HALOX391 (L203 Additive ple 6) ple 7) Zinc Strontium Phosphate) Chromate) NeoCryl XK86 50 50 50 50 Acrylic Resin Halox Flash-X 150 1.0 1.0 1.0 1.0 Anti-flash Rust Agent EFKA3035 Leveling 0.3 0.3 0.3 0.3 Agent ACRYSOLTM 0.2 0.2 0.2 0.2 RM-8W Thickener 100 100 100 100 Rust Level Ri0 Ri0 Ri3 Ri1 Foaming Level 1 0 2 1

[0086] Specific operation: water, bactericide, dispersant, defoamer, wetting agent, bentonite, propylene glycol, film-forming aid, iron red, mica, talcum powder, corrosion resistant agent are pre-dispersed uniformly, and then acrylic resin, leveling agent are added with anti-flash rust agent, dispersed uniformly again; thickener is adopted to adjust viscosity.

[0087] The board may be painted and sprayed according to the test formula given above, placed at room temperature for 7 days, baked at 80° C. for 1 h; and then put in a salt spray box for 300 h. The results show that the treatment of the present disclosure makes the anti-corrosion effect of the water-based acrylic paint significantly improved.

Application Example 5: The Additive with Synergy, Self-Repairing and Anti-Corrosion Applied in Chlorinated Rubber Paint

[0088] Specifically, the anti-corrosion chlorinated rubber paint may be formulated according to the following formula.

TABLE-US-00006 Raw Material {circle around (1)} {circle around (2)} {circle around (3)} CR-20 Chlorinated 23.6 23.6 23.6 Rubber Xylene 25.7 25.7 25.7 42 degree Chlorinated 14.2 14.2 14.2 Paraffin R-902 Titanium Dioxide 20 20 20 Lanninox F Mica Iron 8 8 8 Oxide RM1920 Hydrogenated 0.5 0.5 0.5 Castor Oil Anti-Corrosion Additive 6 6 6 (Exam- (Halox 430 (PC-B-1222 ple 8) modified lead calcium chromate) phosphate) Rust Grade Ri0 Ri1 Ri0 Foaming Level 0 0 0

[0089] Specific operation: the materials in the formula uniformly are mixed and dispersed to prepare the additive.

[0090] The board may be painted and sprayed according to the test formula given above, placed at room temperature for 7 days, and then put in the salt spray box for 1000 hours. The results show that the treatment of the present disclosure makes the anti-corrosion effect of the chlorinated rubber paint significantly improved.

Application Example 6: The Additive with Synergy, Self-Repairing and Anti-Corrosion Applied in Solvent-Based Alkyd Coatings

[0091] Specifically, the anti-corrosive solvent-based alkyd paint may be formulated according to the following formula.

TABLE-US-00007 Raw Material {circle around (1)} {circle around (2)} {circle around (3)} KELSOL ® 3906- 55 55 55 B2G-75 Alkyd Resin BP-183 Organic 0.3 0.3 0.3 Bentonite BP-183 Organic 10 10 10 Bentonite 800 mesh Barium 10 10 10 Sulfate 800 mesh Talcum 9.4 9.4 9.4 Powder Anti-Corrosion 5 5 (Halox 430 5 Additive (Exam- modified (PC-B-1222 ple 9) calcium lead phosphate) chromate) Xylene 4 4 4 No. 200 Solvent 4 4 4 Gasoline Cobalt Manganese 2.2 2.2 2.2 Zirconium Mixed Drier Methyl Ethyl 0.1 0.1 0.1 Ketoxinne Anti-skinning Agent Rust Level Ri0 Ri2 Ri0 Foaming Level 0 2 0

[0092] Specific operation: the materials in the formula are mixed and dispersed uniformly to prepare the additive.

[0093] The board may be painted and sprayed according to the test formula given above, placed at room temperature for 7 days, and then put in the salt spray box for 800 h. The results show that the treatment of the present disclosure makes the anti-corrosion effect of the alkyd paint significantly improved.