Molecular alloy super-wear-resistant coating and preparation method thereof

Abstract

The invention relates to the technical field of coatings, in particular to a molecular alloy super-wear-resistant coating and a preparation method thereof. The component A is prepared from the following components in percentage by weight: 5 to 10 percent of nonylphenol, 5 to 10 percent of catechol, 2 to 5 percent of low-boiling-point aldehyde, 0.3 to 1 percent of acid catalyst, 10 to 15 percent of pigment filler, 10 to 15 percent of wear-resistant filler, 0.3 to 0.8 percent of polyamide wax, 0.3 to 0.8 percent of fumed silica, 3 to 5 percent of solvent, 10 to 15 percent of bisphenol F epoxy resin, 20 to 25 percent of novolac epoxy resin, 0.3 to 0.8 percent of flatting agent and 0.3 to 0.5 percent of defoaming agent; and the component B comprises 5-10% of liquid aromatic amine and 5-10% of alicyclic amine. The coating disclosed by the invention has the comprehensive properties of excellent wear resistance, high adhesive force, compressive strength and the like, and can be applied to the repair of wheel paddle blades, the repair of bearings and the coating of slurry pump pipelines.

Description

Technical Field

[0001] The invention relates to the technical field of coatings, in particular to a molecular alloy super wear-resistant coating and a preparation method thereof. Background Art

[0002] Room temperature curing super wear-resistant coatings have high adhesion, high media resistance, high wear resistance and other properties, so they have many special applications, such as bearing repair, ship blade repair, repair of jacket corrosion leakage in enamel kettle, cement pump pipeline coating. Molecular alloy super wear-resistant coatings have excellent wear resistance, high adhesion, compressive strength and other comprehensive properties. They were first proposed by Bellzona of the United States and promoted for use in repairing damaged metal substrates. At present, the core technology in this field is in Bellzona of the United States and Devonco of the United Kingdom. This type of product has the characteristics of super high wear resistance, adhesion, media resistance, high solid content, etc. There is a blank in this field in China. Summary of the invention

[0003] In order to solve the above technical problems, the purpose of the present invention is to provide a molecular alloy super wear-resistant coating and a preparation method thereof, wherein the coating is used for repairing ship blades, repairing bearings, and coating mud pump pipelines. The coating must meet H10 / 1Kg load / 1000 revolutions, abrasion ≤130mg; metal substrate bonding strength ≥20Mpa; Shore hardness ≥80; no change after 6 months of immersion in hot water at 60℃; no change after 10% sulfuric acid / 50℃ / 7d; no change after immersion in 10% NaOH / 50℃ / 7d solution; no change after immersion in xylene / 50℃ / 7d.

[0004] In order to achieve the above object, the first aspect of the present invention provides a molecular alloy super wear-resistant coating, including component A and component B, which are respectively composed of the following components in the following weight percentages:

[0005] Component A:

[0006] Nonylphenol 5-10%

[0007] Catechol 5-10%

[0008] Low boiling point aldehyde 2-5%

[0009] Acid catalyst 0.3-1%

[0010] Pigments and fillers 10-15%

[0011] Wear-resistant filler 10-15%

[0012] Polyamide wax 0.3-0.8%

[0013] Fumed silica 0.3-0.8%

[0014] Solvent 3-5%

[0015] Bisphenol F epoxy resin 10-15%

[0016] Phenolic epoxy resin 20-25%

[0017] Leveling agent 0.3-0.8%

[0018] Defoaming agent 0.3-0.5%;

[0019] Component B:

[0020] Liquid aromatic amine 5-10%

[0021] Alicyclic amine 5-10%.

[0022] Furthermore, the nonylphenol and catechol can be commercially available products.

[0023] Furthermore, the low-boiling-point aldehyde is an aldehyde compound with a boiling point of 45-70° C., such as liquid aldehydes such as glyoxal, propionaldehyde, isobutyraldehyde, and salicylaldehyde, which can completely separate from the coating after the coating is prepared, thereby improving stability.

[0024] Furthermore, the acid catalyst is selected from acid catalysts that can react with epoxy systems, such as salicylic acid, p-hydroxybenzoic acid, Allnex CYCAT 6395, Allnex CYCAT 4040, and Allnex CYCAT 296-10. Such catalysts can react with epoxy resins during the curing process.

[0025] Furthermore, the pigment filler is a combination of inorganic pigments with good medium resistance (such as iron red, chrome green, titanium dioxide, iron yellow, etc.) and talcum powder and carbon fiber powder. The carbon fiber is T300 produced by Toray of Japan, which is conducive to improving strength. The mass ratio of inorganic pigment, talcum powder and carbon fiber is (1-10): (4-1): 1.

[0026] Furthermore, the wear-resistant filler is one or more of hard fused zirconium oxide, silicon carbide, and first-grade brown corundum in combination with commercially available colloidal graphite powder. The mass ratio of one or more of zirconium oxide, silicon carbide, and first-grade brown corundum to graphite powder is (1-8): (1-2).

[0027] Furthermore, the polyamide wax adopts Crayvallac Super and Crayvallac Ultra of Arkema.

[0028] Furthermore, the fumed silica is hydrophobic silica, such as Evonik Degussa A200, Evonik Degussa R972, R202 and other fumed silica containing silicone-modified fumed silica, and corresponding products of other companies can also be selected, which can effectively improve the wear resistance and smoothness of the coating.

[0029] Furthermore, the solvent is m-xylene, p-xylene or a mixture thereof with an ester solvent; the ester solvent is butyl acetate or ethyl acetate.

[0030] Furthermore, the bisphenol F epoxy resin is a commercially available product, such as Nan Ya 170 resin.

[0031] Furthermore, the phenolic epoxy resin is an epoxy resin with a functionality of less than 3, such as EPALLOY 8240E, 8240, 8250 produced by CVC in the United States, and NPPN 631 of Nanya.

[0032] Furthermore, the defoaming agent is Surfynol 118 of the acetylene alcohol type.

[0033] Furthermore, the leveling agent is an acrylic leveling agent Tilo-L8512, and the solid content is greater than 95%.

[0034] Furthermore, the liquid aromatic amines include liquid aniline, N-methylaniline, R-3200, R-2218B and other liquid amines produced by Rich Chemical (Hubei) Co., Ltd.

[0035] Furthermore, the alicyclic amine adopts common monocyclic alicyclic amines, such as m-cyclohexanediamine (1,3-BAC), isophoronediamine (IPDA), R-2026, R-2028, and R-3600 of Rich Chemical (Hubei) Co., Ltd.

[0036] The present invention provides a method for preparing the molecular alloy super wear-resistant coating as described above, comprising the following steps:

[0037] Nonylphenol, catechol, low boiling point aldehyde, acid catalyst, pigment filler, wear-resistant filler, polyamide wax, fumed silica and solvent are added to a dispersion cylinder for high-speed dispersion, and the temperature reaches 45-65°C / 50min, and phenols and aldehydes react under acid catalysis during the dispersion process; after adding bisphenol F epoxy resin, phenolic epoxy resin, leveling agent and defoaming agent, the temperature is 55-65°C / 30min, and the fineness is checked to reach 30-80 microns to obtain component A. During the addition of epoxy, the ring-opening reaction of part of epoxy with phenolic form to form alcohol hydroxyl group and the reaction of part of aldehydes with phenol to form hydroxymethyl with epoxy alcohol hydroxyl group are tested at 55-65°C to achieve reaction chain extension. At this temperature, aldehydes further react with phenols, and excess aldehydes will gradually volatilize, leaving very little residual aldehydes; liquid aromatic amines and alicyclic amines are mixed and stirred for 15-30min to obtain component B; the prepared components A and B are packaged separately to obtain the molecular alloy super wear-resistant coating.

[0038] Furthermore, the high-speed dispersion speed is 450-500 rpm, and after stirring, the paint generates a vortex in the pull cylinder and the paint does not splash out.

[0039] Nonylphenol, catechol, low-boiling aldehyde, acid catalyst, pigment filler, wear-resistant filler, polyamide wax, fumed silica, solvent, can be sheared to achieve the reaction of phenolic substances with low-boiling aldehyde. Acid catalyst can promote the chain extension of phenolic substances from small molecules to large molecular structures, and produce a large number of hydroxymethyl structures, which help to improve adhesion. Polyamide wax can be activated to produce thixotropy at this temperature; the addition of epoxy resin can achieve the reaction of epoxy resin and phenolic substances under shear conditions. Phenol reacts with epoxy to produce alcohol hydroxyl groups, which can react with hydroxymethyl groups to moderately extend the chain and increase the molecular weight. There will also be a proper amount of hydroxymethyl residues. Hydroxymethyl groups have high adhesion characteristics. Alkynol is used as defoamer because alcohol substances help to improve the stability of hydroxymethyl groups. In addition, acetylene alcohol defoamers have extremely high wetting properties on the substrate. Therefore, the raw materials used can be added step by step according to the reaction sequence to achieve good adhesion and wear resistance.

[0040] Furthermore, the components A and B of the coating are mixed and cured at room temperature for 7 days to obtain a molecular alloy coating.

[0041] The present invention has the advantages that:

[0042] 1. The A and B components of the molecular alloy super-wear-resistant coating of the present invention are mixed according to the mass ratio corresponding to the formula. After curing at room temperature for 7 days, a molecular alloy coating coating can be obtained. The coating meets H10 / 1Kg load / 1000 revolutions, and the wear is ≤130mg; the metal substrate bonding strength is ≥20Mpa; the Shore hardness is ≥80; there is no change after immersion in 60°C hot water for 6 months; there is no change after immersion in 10% sulfuric acid / 50°C / 7d; there is no change after immersion in 10% NaOH / 50°C / 7d solution; there is no change after immersion in xylene / 50°C / 7d.

[0043] 2. The present invention solves the problems of wear resistance and adhesion. The phenolic substances react with the aldehyde substances to form hydroxymethyl groups. The phenolic substances can react with the epoxy resin during the shearing process to increase the molecular weight of the phenolic substances and produce alcoholic hydroxyl groups. The reaction of alcoholic hydroxyl groups with hydroxymethyl groups further increases the crosslinking density, achieving high crosslinking density and high toughness. The amine in component B reacts with the hydroxymethyl groups to catalyze the further reaction of phenol and amine with epoxy to increase the crosslinking density. Compared with pure phenolic substances curing epoxy resin coatings, this method has better toughness and better coating adhesion. DETAILED DESCRIPTION

[0044] The specific implementation methods provided by the present invention are described in detail below in conjunction with examples.

[0045] Embodiment 1:

[0046] Table 1. Coating formula of Example 1

[0047]

[0048] The coating components A and B are mixed in the mass ratio corresponding to the formula, and after curing at room temperature for 7 days, the molecular alloy coating coating can be obtained. The coating meets H10 / 1Kg load / 1000 revolutions, abrasion ≤130mg; metal substrate bonding strength ≥20Mpa; Shore hardness ≥80; no change after immersion in 60℃ hot water for 6 months; no change after immersion in 10% sulfuric acid / 50℃ / 7d; no change after immersion in 10% NaOH / 50℃ / 7d solution; no change after immersion in xylene / 50℃ / 7d.

[0049] Embodiment 2:

[0050] Table 2. Coating formula of Example 2

[0051]

[0052] The coating components A and B are mixed in the mass ratio corresponding to the formula, and after curing at room temperature for 7 days, the molecular alloy coating coating can be obtained. The coating meets H10 / 1Kg load / 1000 revolutions, abrasion ≤130mg; metal substrate bonding strength ≥20Mpa; Shore hardness ≥80; no change after immersion in 60℃ hot water for 6 months; no change after immersion in 10% sulfuric acid / 50℃ / 7d; no change after immersion in 10% NaOH / 50℃ / 7d solution; no change after immersion in xylene / 50℃ / 7d.

[0053] Embodiment 3:

[0054] Table 3. Coating formula of Example 3

[0055]

[0056] The coating components A and B are mixed in the mass ratio corresponding to the formula, and after curing at room temperature for 7 days, the molecular alloy coating coating can be obtained. The coating meets H10 / 1Kg load / 1000 revolutions, abrasion ≤130mg; metal substrate bonding strength ≥20Mpa; Shore hardness ≥80; no change after immersion in 60℃ hot water for 6 months; no change after immersion in 10% sulfuric acid / 50℃ / 7d; no change after immersion in 10% NaOH / 50℃ / 7d solution; no change after immersion in xylene / 50℃ / 7d.

[0057] Embodiment 4:

[0058] Table 4. Coating formula of Example 4

[0059]

[0060] The coating components A and B are mixed in the mass ratio corresponding to the formula, and after curing at room temperature for 7 days, the molecular alloy coating coating can be obtained. The coating meets H10 / 1Kg load / 1000 revolutions, abrasion ≤130mg; metal substrate bonding strength ≥20Mpa; Shore hardness ≥80; no change after immersion in 60℃ hot water for 6 months; no change after immersion in 10% sulfuric acid / 50℃ / 7d; no change after immersion in 10% NaOH / 50℃ / 7d solution; no change after immersion in xylene / 50℃ / 7d.

[0061] Embodiment 5:

[0062] Table 5. Coating formula of Example 5

[0063]

[0064] The coating components A and B are mixed in the mass ratio corresponding to the formula, and after curing at room temperature for 7 days, the molecular alloy coating coating can be obtained. The coating meets H10 / 1Kg load / 1000 revolutions, abrasion ≤130mg; metal substrate bonding strength ≥20Mpa; Shore hardness ≥80; no change after immersion in 60℃ hot water for 6 months; no change after immersion in 10% sulfuric acid / 50℃ / 7d; no change after immersion in 10% NaOH / 50℃ / 7d solution; no change after immersion in xylene / 50℃ / 7d.

[0065] Embodiment 6:

[0066] Table 6. Coating formula of Example 6

[0067]

[0068] The coating components A and B are mixed in the mass ratio corresponding to the formula, and after curing at room temperature for 7 days, the molecular alloy coating coating can be obtained. The coating meets H10 / 1Kg load / 1000 revolutions, abrasion ≤130mg; metal substrate bonding strength ≥20Mpa; Shore hardness ≥80; no change after immersion in 60℃ hot water for 6 months; no change after immersion in 10% sulfuric acid / 50℃ / 7d; no change after immersion in 10% NaOH / 50℃ / 7d solution; no change after immersion in xylene / 50℃ / 7d.

[0069] The preferred embodiments of the present invention have been specifically described above, but the present invention is not limited to the embodiments. Those skilled in the art may make various equivalent modifications or substitutions without violating the spirit of the present invention. These equivalent modifications or substitutions are all included in the scope defined by the claims of this application.

Claims

1. A molecular alloy super wear-resistant coating, characterized in that: It includes component A and component B, which are respectively composed of the following ingredients in the following weight percentages: Component A: Nonylphenol 5-10% Catechol 5-10% Low boiling point aldehyde 2-5% Acid catalyst 0.3-1% Pigments and fillers 10-15% Wear-resistant filler 10-15% Polyamide wax 0.3-0.8% Fumed silica 0.3-0.8% Solvent 3-5% Bisphenol F epoxy resin 10-15% Phenolic epoxy resin 20-25% Leveling agent 0.3-0.8% Defoaming agent 0.3-0.5%; Component B: Liquid aromatic amine 5-10% Alicyclic amine 5-10%.

2. The molecular alloy super wear-resistant coating according to claim 1, characterized in that: The low boiling point aldehydes are aldehyde compounds with a boiling point of 45-70° C., such as glyoxal, propionaldehyde, isobutyraldehyde and salicylaldehyde.

3. The molecular alloy super wear-resistant coating according to claim 1, characterized in that: The acid catalyst is selected from salicylic acid, p-hydroxybenzoic acid, Allnex CYCAT 6395, Allnex CYCAT 4040, and Allnex CYCAT 296-10.

4. The molecular alloy super wear-resistant coating according to claim 1, characterized in that: The color filler is an inorganic pigment with good medium resistance, a combination of talcum powder and carbon fiber. The inorganic pigment is selected from iron red, chrome green, titanium dioxide, and iron yellow. The carbon fiber is T300 from Japan Toray. The wear-resistant filler is a combination of one or more of hard fused zirconium oxide, silicon carbide, and first-grade brown corundum and colloidal graphite powder.

5. The molecular alloy super wear-resistant coating according to claim 1, characterized in that: The polyamide wax is Crayvallac Super and Crayvallac Ultra of Arkema; ​​the fumed silica is selected from A200 of Evonik Degussa, R972 and R202 of Evonik Degussa.

6. The molecular alloy super wear-resistant coating according to claim 1, characterized in that: The solvent is m-xylene, p-xylene or a mixture thereof with an ester solvent; the ester solvent is butyl acetate or ethyl acetate.

7. The molecular alloy super wear-resistant coating according to claim 1, characterized in that: The bisphenol F epoxy resin is Nan Ya 170 resin; the phenolic epoxy resin is EPALLOY 8240E, 8240, 8250 and Nan Ya NPPN 631 produced by CVC of the United States.

8. The molecular alloy super wear-resistant coating according to claim 1, characterized in that: The defoamer is Surfynol 118 of acetylene alcohol type; the leveling agent is Tilo-L8512 of acrylic ester type, with a solid content of more than 95%.

9. The molecular alloy super wear-resistant coating according to claim 1, characterized in that: The liquid aromatic amines include liquid aniline, N-methylaniline, R-3200 and R-2218B of Rich Chemical (Hubei) Co., Ltd.; the alicyclic amines include m-cyclohexanediamine (1,3-BAC), isophoronediamine (IPDA), R-2026, R-2028 and R-3600 of Rich Chemical (Hubei) Co., Ltd.

10. A method for preparing a molecular alloy super wear-resistant coating according to any one of claims 1 to 9, characterized in that: The following steps are involved: Nonylphenol, catechol, low boiling point aldehyde, acid catalyst, pigment filler, wear-resistant filler, polyamide wax, fumed silica and solvent are added into a dispersion cylinder for high-speed dispersion, and the temperature reaches 45-65°C / 50min. After adding bisphenol F epoxy resin, phenolic epoxy resin, leveling agent and defoaming agent, the temperature is 55-65°C / 30min, and the fineness is checked to reach 30-80 microns to obtain component A. Liquid aromatic amine and alicyclic amine are mixed and stirred for 15-30min to obtain component B. The prepared components A and B are packaged separately to obtain the molecular alloy super wear-resistant coating.

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