Anticorrosive paint as well as preparation method and application thereof

Abstract

The invention discloses an anticorrosive coating as well as a preparation method and application thereof. The anticorrosive paint is composed of a component A and a component B in a weight ratio of 100: (5-15), wherein the component A is prepared from the following components in percentage by mass: 30 to 45 percent of matrix resin, 0.3 to 1 percent of adhesion promoter, 0.1 to 1 percent of rheological additive, 40 to 55 percent of pigment filler and 10 to 25 percent of first solvent; the matrix resin is a mixture of acrylic modified epoxy resin, thermoplastic acrylic resin and first epoxy resin; wherein the acrylic acid modified epoxy resin is prepared by performing esterification reaction on second epoxy resin and acrylic acid or methacrylic acid. When the anticorrosive paint is used for coating or maintaining ocean engineering equipment or ocean facilities (such as ships), a good anticorrosive effect can be provided, and the anticorrosive paint has good bonding capacity with antifouling paint.

Description

Technical Field

[0001] The present invention relates to the technical field of chemical materials, and more specifically, to an anti-corrosion coating and a preparation method and application thereof. Background Art

[0002] In the modern ship repair industry, the selection and application of coatings not only affects the maintenance cost and efficiency of ships, but also directly affects the performance and operating costs of ships. With the development of science and technology and the increase in market demand, ship repair yards have put forward new requirements for coatings to adapt to stricter environmental protection standards, improve coating performance and save construction time. On the premise of meeting performance, reducing the amount of coating and shortening the construction period will be the future development direction.

[0003] At present, the supporting system of underwater anti-corrosion and anti-fouling coatings is an anti-rust coating, a connecting paint, and an anti-fouling coating. Because the anti-rust coating is generally a two-component epoxy system, and the self-polishing anti-fouling paint is an acrylic system, the properties, preparation methods, and coating processes of the materials selected for the two are different. These differences can easily cause defects to form between the coating interfaces, causing the anti-fouling coating to fall off during the application process. Usually, a connecting paint is required between the anti-rust coating and the anti-fouling coating to enhance the adhesion of the two coatings. This method undoubtedly increases the difficulty and cost of ship painting. Summary of the invention

[0004] Based on the above facts, the purpose of the present invention is to provide an anticorrosive coating and a preparation method and application thereof. The anticorrosive coating has excellent anticorrosion effect, and when used in the coating or maintenance of marine engineering equipment or marine facilities (such as ships), it can provide good anticorrosion effect and has good bonding ability with antifouling coating.

[0005] In order to achieve the above object, the present invention adopts the following technical solutions:

[0006] In one aspect, the present invention provides an anticorrosive coating, which is composed of a component A and a component B in a weight ratio of 100:(5-15); wherein:

[0007] The component A comprises the following components by weight percentage:

[0008] 30-45% base resin, 0.3-1% adhesion promoter, 0.1-1% rheological additive, 40-55% pigment and filler, and 10-25% first solvent;

[0009] The matrix resin is a mixture of acrylic modified epoxy resin, thermoplastic acrylic resin and first epoxy resin;

[0010] Wherein, the acrylic modified epoxy resin is prepared by esterification reaction of a second epoxy resin with acrylic acid or methacrylic acid;

[0011] The component B comprises the following components by weight percentage:

[0012] 65-75% of amine curing agent, 1-3% of curing accelerator and 23-33% of second solvent.

[0013] Furthermore, the mass ratio of the first epoxy resin, the thermoplastic acrylic resin and the acrylic modified epoxy resin is 100:(30-70):(10-30).

[0014] Furthermore, the mass ratio of the first epoxy resin, the thermoplastic acrylic resin and the acrylic modified epoxy resin is 100:(40-70):(10-30).

[0015] Furthermore, the mass ratio of the first epoxy resin, the thermoplastic acrylic resin and the acrylic modified epoxy resin is 100:(45-65):(15-25).

[0016] Furthermore, during the preparation of the acrylic modified epoxy resin, the molar ratio of the second epoxy resin to acrylic acid or methacrylic acid is 1:1 to 1:3.

[0017] Furthermore, during the preparation of the acrylic modified epoxy resin, the molar ratio of the second epoxy resin to acrylic acid or methacrylic acid is 1:1.9 to 1:2.1.

[0018] Furthermore, during the preparation of the acrylic modified epoxy resin, the molar ratio of the second epoxy resin to acrylic acid or methacrylic acid is 1:1.9.

[0019] Furthermore, the temperature of the esterification reaction is 80 to 120° C., and the time of the esterification reaction is 2 to 6 hours.

[0020] Furthermore, the temperature of the esterification reaction is 90-110°C.

[0021] Furthermore, the esterification reaction time is 4 hours.

[0022] Furthermore, the solubility parameter (SP) of the first epoxy resin is 10.2-12.

[0023] Furthermore, the solubility parameter of the first epoxy resin is 10.5-11.5.

[0024] Furthermore, the weight average molecular weight of the first epoxy resin is 250 to 2500 g / mol.

[0025] Furthermore, the weight average molecular weight of the first epoxy resin is 350 to 1500 g / mol.

[0026] Furthermore, the epoxy equivalent of the first epoxy resin is 100 to 3000 g / equivalent.

[0027] Furthermore, the epoxy equivalent of the first epoxy resin is 150 to 1000 g / equivalent.

[0028] Furthermore, the first epoxy resin is selected from one or more of bisphenol A epoxy resin, bisphenol F epoxy resin, bisphenol AD ​​epoxy resin, bisphenol S epoxy resin, biphenyl epoxy resin and rubber modified epoxy resin.

[0029] Furthermore, the solubility parameter of the thermoplastic acrylic resin is 9.2-12.

[0030] Furthermore, the solubility parameter of the thermoplastic acrylic resin is 9.6 to 11.5.

[0031] Furthermore, the glass transition temperature of the thermoplastic acrylic resin is 40 to 90°C.

[0032] Furthermore, the glass transition temperature of the thermoplastic acrylic resin is 60-72°C.

[0033] Furthermore, the weight average molecular weight of the thermoplastic acrylic resin is 1000 to 90000 g / mol.

[0034] Furthermore, the weight average molecular weight of the thermoplastic acrylic resin is 1000 to 60000 g / mol.

[0035] Furthermore, the absolute value of the difference between the solubility parameters of the thermoplastic acrylic resin and the first epoxy resin is less than 2.5.

[0036] Furthermore, the thermoplastic acrylic resin is a (meth)acrylic acid homopolymer or a (meth)acrylic acid copolymer containing a structural unit derived from (meth)acrylic acid ester.

[0037] Furthermore, the thermoplastic acrylic resin is obtained by free radical polymerization of acrylic monomers.

[0038] Furthermore, the polymerization temperature of the free radical polymerization is 90 to 110° C., and the polymerization time is 3 to 8 hours.

[0039] Further, the acrylic monomer is selected from one or more of n-butyl acrylate (n-BA), methyl methacrylate (MMA), styrene (ST), ethyl acrylate (EA), n-butyl methacrylate (n-MBA), 2-ethylhexyl methacrylate (EHMA), 2-hydroxyethyl methacrylate (HEMA) and hydroxyethyl acrylate (HEA).

[0040] Furthermore, in the component B, the amine curing agent is compounded by a modified polyamide curing agent having an amine value of 210-230 mgKOH / g and a modified polyamide curing agent having an amine value of 160-200 mgKOH / g.

[0041] Furthermore, the modified polyamide curing agent with an amine value of 210-230 mgKOH / g is an adduct of aliphatic polyamide modified by dimer acid and epoxy resin.

[0042] Furthermore, the modified polyamide curing agent having an amine value of 160-200 mgKOH / g is a dimer acid-modified aliphatic polyamide, and the amine value of the dimer acid-modified aliphatic polyamide is preferably 180-200 mgKOH / g or 165-185 mgKOH / g.

[0043] Furthermore, the mixing ratio of the modified polyamide curing agent having an amine value of 210-230 mgKOH / g and the modified polyamide curing agent having an amine value of 160-200 mgKOH / g is 1:(0.5-1.5).

[0044] In another aspect, the present invention provides a method for preparing the anticorrosive coating as described above, the preparation method comprising the following steps:

[0045] The preparation of component A comprises the following steps:

[0046] The base resin, the first solvent, the adhesion promoter, and the pigment are mixed, and then the rheological additive is added, mixed and dispersed to a fineness of less than 60 μm to obtain the component A;

[0047] The preparation of component B comprises the following steps:

[0048] The amine curing agent, the curing accelerator and the second solvent are mixed to obtain the component B.

[0049] In yet another aspect, the present invention provides use of the anti-corrosion coating as described above in the protection of marine engineering equipment or marine facilities.

[0050] Furthermore, the anti-corrosion coating is applied to the marine engineering equipment or marine facilities.

[0051] Furthermore, the coating of the marine engineering equipment or marine facilities includes:

[0052] The anti-corrosion coating and anti-fouling coating are sequentially applied to the parts of the marine engineering equipment or marine facilities that need to be painted or protected from fouling.

[0053] The beneficial effects of the present invention are as follows:

[0054] In the anticorrosive coating provided by the present invention, the introduction of acrylic modified epoxy resin improves the compatibility of epoxy resin and acrylic resin. The epoxy group at one end of the acrylic modified epoxy resin structure is cross-linked and cured with a curing agent to form a three-dimensional space network, which has good anticorrosion performance and substrate adhesion performance. The other acrylic acid group in the acrylic modified epoxy resin structure has good compatibility with the acrylic resin in the antifouling coating, and can establish a more excellent interface bonding effect. Ultimately, while achieving an effective transition from substrate / anticorrosive primer to antifouling coating, the problem of poor adhesion between different coatings caused by the matching and use of coatings, the interface morphology of the coating system, performance defects and large-area shedding is effectively solved. BRIEF DESCRIPTION OF THE DRAWINGS

[0055] The specific implementation modes of the present invention are further described in detail below in conjunction with the accompanying drawings.

[0056] Figure 1 A schematic diagram of an exemplary apparatus for preparing an acrylic modified epoxy resin in the present invention is shown. DETAILED DESCRIPTION

[0057] In order to more clearly illustrate the present invention, the present invention is further described below in conjunction with preferred embodiments and accompanying drawings. Similar components in the accompanying drawings are represented by the same reference numerals. It should be understood by those skilled in the art that the content specifically described below is illustrative rather than restrictive, and should not be used to limit the scope of protection of the present invention.

[0058] In order to obtain an anticorrosive coating which has both anticorrosion properties and good inter-coating bonding ability with an antifouling coating (antifouling topcoat) and can be used for coating marine engineering equipment or marine facilities (such as ships), the present invention provides an anticorrosive coating, characterized in that the anticorrosive coating is composed of a component A and a component B in a weight ratio of 100:(5-15); wherein,

[0059] The component A comprises the following components by weight percentage:

[0060] 30-45% base resin, 0.3-1% adhesion promoter, 0.1-1% rheological additive, 40-55% pigment and filler, and 10-25% first solvent;

[0061] The matrix resin is a mixture of acrylic modified epoxy resin, thermoplastic acrylic resin and first epoxy resin;

[0062] Wherein, the acrylic modified epoxy resin is prepared by esterification reaction of a second epoxy resin with acrylic acid or methacrylic acid;

[0063] The component B comprises the following components by weight percentage:

[0064] 65-75% of amine curing agent, 1-3% of curing accelerator and 23-33% of second solvent.

[0065] The anticorrosive coating can be used as original paint or as repair paint. When used in a water environment, especially in a marine environment, the anticorrosive coating has a good anticorrosive effect. At the same time, it can be directly combined with the antifouling coating (no additional coating as a connecting layer is required between the two) and has high bonding adhesion, which can well prevent the antifouling coating from falling off. In addition, when the anticorrosive coating is used, it has a very short surface drying time and actual drying time. When used for painting and repairing ships, it can well shorten the ship repair construction period.

[0066] In some preferred examples, in the component A, the amount of base resin added includes but is not limited to 30-40%, 35-40%, 36%, etc., calculated by mass percentage; in some other preferred examples, in the component A, the amount of color and filler added includes but is not limited to 45-50%, 48-50%, 48.2%, etc., calculated by mass percentage.

[0067] In addition, it should be noted that the "first" and "second" in "first epoxy resin" and "second epoxy resin" have no other meanings and are only used to distinguish more directly; the first epoxy resin and the second epoxy resin may be the same or different. Similarly, the "first" and "second" in the "first solvent" and "second solvent" have no other meanings and are only used to distinguish more directly.

[0068] In some specific examples, the mass ratio of the first epoxy resin, the thermoplastic acrylic resin and the acrylic modified epoxy resin is 100:(30-70):(10-30). By matching the three resins in specific proportions, the compatibility of the coating system can be improved, and the anti-corrosion coating has a faster surface drying time and actual drying time under the condition of good anti-rust and anti-corrosion performance, so that the anti-fouling topcoat and anti-corrosion primer have better adhesion. In some preferred examples, the mass ratio of the first epoxy resin, the thermoplastic acrylic resin and the acrylic modified epoxy resin includes but is not limited to 100:(40-70):(10-30), 100:(45-65):(15-25), 100:(50-65):(15-25), 100:(50-60):(15-20), 100:60:20, etc.

[0069] In some examples, during the preparation of the acrylic modified epoxy resin, the molar ratio of the second epoxy resin to acrylic acid or methacrylic acid is 1:1 to 1:3, preferably 1:1.9 to 1:2.1. In some specific examples, the molar ratio of the second epoxy resin to acrylic acid or methacrylic acid includes but is not limited to 1:1.9 to 1:2, 1:2 to 1:2.1, 1:1.9, etc.

[0070] In some preferred examples, during the preparation of the acrylic modified epoxy resin, the mass ratio of the second epoxy resin to acrylic acid or methacrylic acid is 100:(35-45). More specifically, the mass ratio of the second epoxy resin to acrylic acid or methacrylic acid includes but is not limited to 100:(35-42), 100:(36.5-40.5), 100:(36.5-38.5), 100:(38.5-40.5), 100:36.5, 100:38.5, 100:40.5, etc. The prepared acrylic modified epoxy resin has a high solid content, a suitable viscosity and a high glass transition temperature.

[0071] In some examples, the temperature of the esterification reaction is 80-120° C., more preferably 90-110° C., and the time of the esterification reaction is 2-6 hours, preferably 4 hours. Under these conditions, the reaction speed can be avoided to be too fast and produce side reactions, so that acrylic acid or methacrylic acid has a higher conversion rate.

[0072] In some preferred examples, the preparation of the acrylic modified epoxy resin comprises the following steps:

[0073] Add the second epoxy resin and part of the third solvent into a clean and dry four-necked flask, mix the materials evenly under stirring and heat to 80-100°C (preferably 90°C), then slowly drop a mixture of acrylic acid or methacrylic acid, a catalyst, an inhibitor and the remaining third solvent from a constant pressure dropping funnel, and complete the dropwise addition within 0.5h; after the dropwise addition is completed, slowly heat up to the reaction temperature (preferably 100-110°C) and keep warm, cool down after the reaction is kept warm to terminate the reaction, and obtain an acrylic acid-modified epoxy resin, and transfer the product into a brown bottle for standby use after the product is cooled.

[0074] In some specific examples, the catalyst includes but is not limited to tertiary amines, quaternary ammonium salts, etc. Specifically, one of triethylamine, N,N-dimethylaniline, trimethylbenzyl ammonium chloride, triphenylphosphine, triphenylantimony, chromium acetylacetonate, tetraethylammonium bromide, etc. is included, preferably N,N-dimethylaniline. Exemplarily, the catalyst accounts for 0.1 to 3 wt% of the raw material amount in the preparation of acrylic modified epoxy resin, preferably 1 to 3 wt%, 1 to 2 wt%, etc.

[0075] In some specific examples, the polymerization inhibitor includes but is not limited to p-hydroxybenzene methane, hydroquinone, 2,5-dimethyl hydroquinone, 2,6-di-tert-butyl hydroquinone, etc., preferably hydroquinone. Exemplarily, the polymerization inhibitor accounts for 0.01-1wt% of the raw material used in the preparation of the acrylic modified epoxy resin, preferably 0.1-0.3wt%, 0.1-0.2wt%, etc.

[0076] In some specific examples, the third solvent includes but is not limited to xylene and / or n-butanol.

[0077] In some more specific examples, the third solvent is a mixture of xylene and n-butanol in a mass ratio of 6:4, and its content is 20-35wt% of the total amount of raw materials in the preparation of acrylic modified epoxy resin, preferably 25-30wt%.

[0078] In some more specific examples, the remaining third solvent is xylene, and the amount thereof is 1 to 5 wt %, preferably 1 to 3 wt %, of the total amount of raw materials in the preparation of the acrylic modified epoxy resin.

[0079] In some specific examples, the second epoxy resin includes but is not limited to E-51 epoxy resin and the like.

[0080] In the preparation process of acrylic modified epoxy resin, by controlling the selection, dosage and specific reaction conditions of raw material components, the obtained acrylic modified epoxy resin is used in the anti-corrosion coating described in this embodiment, which improves the compatibility of the resin system in the anti-corrosion coating, so that the anti-corrosion coating can be better directly and firmly combined with the anti-fouling coating, while shortening the surface drying time and actual drying time during actual construction.

[0081] In some examples, in the component A, the content of the acrylic modified epoxy resin, calculated by mass percentage, includes but is not limited to 2-8wt%, 4-8wt%, 4-6wt%, 4wt%, etc.

[0082] From the viewpoint of improving shrinkage resistance and interlayer adhesion, in some examples, the solubility parameter SP (hereinafter, also referred to as "SP") of the first epoxy resin in the anticorrosive coating is preferably 10.2 to 12, more preferably 10.5 to 11.5; the weight average molecular weight (hereinafter, also referred to as "Mw") is 250 to 2500 g / mol, preferably 350 to 1500 g / mol. The weight average molecular weight refers to the value obtained by converting the molecular weight measured by gel permeation chromatography (GPC) based on the molecular weight of polystyrene.

[0083] In the present specification, the solubility parameter SP of a resin can be measured by the following method (reference: SUH, CLARKE, JPSA-1, 5, 1671 to 1681 (1967)).

[0084] At a measurement temperature of 20°C, weigh 0.5g of resin into a 100mL beaker, add 10mL of a good solvent (acetone) using a hole pipette, and dissolve it using a magnetic stirrer to prepare a dilute solution. Next, use a 50mL burette to slowly drop a low SP poor solvent (n-hexane) into the dilute solution, and take the point at which the dilute solution becomes turbid as the amount of low SP poor solvent added. In addition, slowly drop a high SP poor solvent (ion exchange water) into the above-mentioned dilute solution, and take the point at which the dilute solution becomes turbid as the amount of high SP poor solvent added. The SP value can be calculated by the known calculation method described in the above-mentioned references, etc., from the amount of each of the above-mentioned poor solvents added until the turbidity point is reached.

[0085] In some examples, the epoxy equivalent of the first epoxy resin is 100 to 3000 g / equivalent, preferably 150 to 1000 g / equivalent, and more preferably 180 to 500 g / equivalent. Under this condition, it is easy to obtain a good curing tendency, and the toughness of the obtained coating film tends to become good. If the epoxy equivalent is too large, there is a tendency that the curing property becomes poor and the coating film tends to harden easily.

[0086] In some examples, the first epoxy resin is selected from one or more of bisphenol A epoxy resin, bisphenol F epoxy resin, bisphenol AD ​​epoxy resin, bisphenol S epoxy resin, biphenyl epoxy resin and rubber modified epoxy resin. The first epoxy resin can improve the corrosion resistance of the anti-corrosion coating and has good adhesion to the substrate.

[0087] In some specific examples, the first epoxy resin includes but is not limited to E-51 epoxy resin and the like.

[0088] In some examples, the component A contains 5-45wt% of the first epoxy resin by weight percentage. In some specific examples, the content of the first epoxy resin includes but is not limited to 15-45wt%, 15-30wt%, 15-25wt%, 15-20wt%, etc. If the amount of the first epoxy resin added is too small, the anti-corrosion performance of the anti-corrosion coating will be affected.

[0089] Considering the compatibility with the first epoxy resin, in some examples, the solubility parameter of the thermoplastic acrylic resin is 9.2 to 12, preferably 9.6 to 11.5.

[0090] From the viewpoint of improving the spacer adhesion, in some examples, the absolute value of the difference in solubility parameter between the thermoplastic acrylic resin and the first epoxy resin is 2.5 or less.

[0091] In some examples, the glass transition temperature (Tg) of the thermoplastic acrylic resin is 40 to 90° C., preferably 60 to 72° C. Under this condition, the anticorrosive coating obtained has good interlayer adhesion and shrinkage resistance with other coatings. If the Tg of the thermoplastic acrylic resin is too low, the coating film is easy to soften, and therefore, there is an unfavorable tendency in improving interlayer adhesion and shrinkage resistance; if the Tg of the thermoplastic acrylic resin is too high, the coating film is easy to crack, and there is an unfavorable tendency in improving interlayer adhesion and shrinkage resistance.

[0092] In this specification, the glass transition temperature is a temperature measured using a differential scanning calorimeter (DSC) in accordance with JIS K 7121.

[0093] In some examples, the weight average molecular weight of the thermoplastic acrylic resin is 1000 to 90000 g / mol, preferably 1000 to 60000 g / mol. Under this condition, it is more helpful to obtain an anticorrosive coating with moderate viscosity and good curing properties; in addition, under this condition, the adhesion between the coating layers and the shrinkage resistance of the paint film can be better improved.

[0094] In some examples, the solid content of the thermoplastic acrylic resin includes but is not limited to 40-100 wt %, 40-60 wt %, 40-50 wt %, 50 wt %, etc.

[0095] In some examples, the thermoplastic acrylic resin is a (meth)acrylic acid homopolymer or a (meth)acrylic acid copolymer including a structural unit derived from (meth)acrylic acid ester.

[0096] In some examples, the thermoplastic acrylic resin is obtained by free radical polymerization of acrylic monomers, with a polymerization temperature of 90 to 110° C. and a polymerization time of 3 to 8 hours, preferably 3 to 5 hours.

[0097] In some examples, the acrylic monomer is selected from one or more of n-butyl acrylate (n-BA), methyl methacrylate (MMA), styrene (ST), ethyl acrylate (EA), n-butyl methacrylate (n-MBA), 2-ethylhexyl methacrylate (EHMA), 2-hydroxyethyl methacrylate (HEMA) and hydroxyethyl acrylate (HEA).

[0098] In some specific examples, the acrylic monomer is a mixture of methyl methacrylate, n-butyl acrylate, ethyl acrylate and 2-hydroxyethyl methacrylate in a mass ratio of 5:(2-3):1:(5-6); or, the acrylic monomer is a mixture of methyl methacrylate, n-butyl acrylate, styrene and 2-hydroxyethyl methacrylate in a mass ratio of (12-13):1:3:(7-8); or, the acrylic monomer is a mixture of methyl methacrylate, n-butyl acrylate, styrene and ethyl acrylate in a mass ratio of (1-3):1:(2-4.5):(0.1-0.5); or, the acrylic monomer is a mixture of n-butyl acrylate, styrene, ethyl acrylate and 2-hydroxyethyl methacrylate in a mass ratio of 1:(8-9):(3-4):(1-2); or, the acrylic monomer is a mixture of n-butyl acrylate, styrene and 2-hydroxyethyl methacrylate in a mass ratio of 1:5.5:3.5. At this time, the thermoplastic acrylic resin obtained by free radical polymerization is used to prepare the anti-corrosion coating, which has better interlayer adhesion, anti-corrosion effect and structural stability.

[0099] In some more specific examples, the preparation of the thermoplastic acrylic resin comprises the following steps:

[0100] A solvent (e.g., xylene) is added to a four-necked flask equipped with a thermometer, a cooling tube, a stirrer, a dropping funnel, a nitrogen inlet tube, and a temperature controller, and the temperature is maintained at 90-110° C. (preferably 110° C.); then, a mixed solution of acrylic monomer and a free radical polymerization initiator (e.g., tert-butyl peroxy-2-ethylhexanoate) is added to the dropping funnel, and the mixture is dropped into the four-necked flask at a constant rate for 3-4 hours (preferably 3 hours), and after the dropping is completed, the mixture is kept warm for 30 minutes to 1 hour (preferably 30 minutes) to obtain the thermoplastic acrylic resin.

[0101] In the preparation of some specific thermoplastic acrylic resins, the raw materials contain 40-60 wt % of acrylic monomer, 38-58 wt % of solvent and 1-3 wt % of free radical polymerization initiator, calculated by mass percentage.

[0102] In some examples, the component A contains 1 to 40 wt% of thermoplastic acrylic resin by weight percentage. In some specific examples, the content of thermoplastic acrylic resin includes but is not limited to 2 to 18 wt%, 10 to 18 wt%, 10 to 15 wt%, 10 to 12 wt%, etc. Under this condition, the adhesion and shrinkage resistance of the paint film can be better improved.

[0103] In some examples, the rheological additive includes, but is not limited to, one or more of polyamide wax, hydrogenated castor oil, and fumed silica.

[0104] The color filler includes fillers and pigments. In some examples, the filler includes but is not limited to one of micaceous iron ash, barium sulfate, feldspar powder, mica powder, and talcum powder; the pigment includes but is not limited to one or more of iron red, high titanium yellow, high titanium gray, and lemon yellow.

[0105] In some examples, the first solvent includes but is not limited to a combination of two or more of aromatic hydrocarbons, esters, alcohols, and ketones, and preferably a combination of two or more of xylene, n-butanol, butyl acetate, isobutanol, and methyl isobutyl ketone.

[0106] In some examples, in the component B, the amine curing agent is one or more of a polyamine curing agent, a modified polyamine curing agent, a polyamide curing agent, and a modified polyamide curing agent.

[0107] Examples of the polyamine curing agent include aliphatic polyamines (meta-xylene diamine, isophorone diamine, diethylene triamine, triethylene tetramine, diamino diphenyl methane, etc.); alicyclic polyamines; and aromatic polyamines.

[0108] The modified polyamine curing agent is a modified product of the above-mentioned polyamine, and examples thereof include aliphatic, alicyclic or aromatic polyamines modified by epoxide addition, Michael addition, Mannich addition, thiourea addition, acrylonitrile addition, ketone end-capping or the like.

[0109] Examples of polyamide curing agents include polyamides produced by condensation of dimer acid and polyamine and having reactive primary and secondary amino groups in the molecule. The polyamines forming the polyamides may be the above-mentioned aliphatic polyamines, alicyclic polyamines, aromatic polyamines, and the like.

[0110] The modified polyamide curing agent is a modified product of polyamide, and examples thereof include epoxy adducts obtained by adding an epoxy compound to polyamide, Mannich modified products of modified polyamide, dimer acid-modified aliphatic polyamide, and adducts of dimer acid-modified aliphatic polyamide and epoxy resin.

[0111] In some preferred examples, the amine curing agent is compounded by a modified polyamide curing agent having an amine value of 210-230 mgKOH / g and a modified polyamide curing agent having an amine value of 160-200 mgKOH / g.

[0112] In some preferred examples, the modified polyamide curing agent with an amine value of 210-230 mgKOH / g is an adduct of aliphatic polyamide modified by dimer acid and epoxy resin.

[0113] In some preferred examples, the modified polyamide curing agent having an amine value of 160-200 mgKOH / g is a dimer acid-modified aliphatic polyamide, and the amine value of the dimer acid-modified aliphatic polyamide is preferably 180-200 mgKOH / g or 165-185 mgKOH / g.

[0114] In some preferred examples, the mixing ratio of the modified polyamide curing agent having an amine value of 210-230 mgKOH / g and the modified polyamide curing agent having an amine value of 160-200 mgKOH / g is 1:(0.5-1.5).

[0115] By compounding two different amine curing agents, the coating film is given a short surface drying time and actual drying time, as well as better anti-corrosion performance and adhesion with antifouling coatings.

[0116] In some examples, a tertiary amine curing accelerator may be used as the curing accelerator, and examples of the tertiary amine curing accelerator include 2,4,6-tris(dimethylaminomethyl)phenol (TAP), dimethylaminoethanol (DMAE), N,N-dimethylaniline (DMA), triethanolamine, triethylenediamine (1,4-diazabicyclo(2,2,2)octane), and the like.

[0117] The anti-corrosion coating of this embodiment has both anti-corrosion and transition connection functions (directly combined with the anti-fouling coating). The preferred acrylic modified epoxy resin improves the compatibility of the resin system, and the ratio range between the acrylic modified epoxy resin, the thermoplastic acrylic resin and the first epoxy resin is preferably controlled. It is preferably matched with two or more amine curing agents, so that the coating formed by the prepared anti-corrosion coating has an optimal faster drying speed and good anti-shrinkage performance. It meets the performance indicators of the anti-corrosion coating while increasing the bonding strength with the anti-fouling coating, greatly shortening the coating construction cycle.

[0118] According to another specific embodiment of the present invention, a method for preparing the anti-corrosion coating is provided, which comprises the following steps:

[0119] The preparation of component A comprises the following steps:

[0120] The base resin, the first solvent, the adhesion promoter, and the pigment are mixed, and then the rheological additive is added, mixed and dispersed to a fineness of less than 60 μm to obtain the component A;

[0121] The preparation of component B comprises the following steps:

[0122] The amine curing agent, the curing accelerator and the second solvent are mixed to obtain the component B.

[0123] According to another specific embodiment of the present invention, there is provided application of the anti-corrosion coating in the protection of marine engineering equipment or marine facilities.

[0124] In some examples, the anti-corrosion coating is applied to the marine engineering equipment or marine facilities.

[0125] In some examples, the coating of the marine engineering equipment or marine facilities includes:

[0126] The anti-corrosion coating and anti-fouling coating are sequentially applied to the parts of the marine engineering equipment or marine facilities that need to be painted or protected from fouling.

[0127] Furthermore, the antifouling paint contains acrylic resin.

[0128] The technical solution of the present invention is described below in conjunction with some specific embodiments:

[0129] The specific examples are as follows, wherein the preparation method of acrylic modified epoxy resin is detailed in Examples 1-3, and the schematic diagram of the synthesis device is as follows Figure 1 shown.

[0130] Example 1

[0131] A method for preparing an acrylic acid-modified epoxy resin (acrylic acid-modified epoxy resin-1) comprises the following steps:

[0132] In a clean and dry 500ml four-necked flask, add 100g E-51 epoxy resin and 60.5g mixed solvent of xylene / n-butanol (the mass ratio of xylene to n-butanol is 6:4), mix all the materials evenly under stirring conditions and heat to 90°C, maintain this temperature, mix 36.5g acrylic acid, 3g N,N-dimethylaniline, 0.3g hydroquinone and 3g xylene evenly in advance for use, then slowly add the mixture dropwise from a constant pressure dropping funnel and finish dropping within 0.5h; after finishing dropping, slowly heat to 110°C and keep warm for 3h, then cool down to terminate the reaction, and after cooling the product, transfer it into a brown bottle to obtain acrylic acid-modified epoxy resin-1.

[0133] Example 2

[0134] A method for preparing an acrylic acid-modified epoxy resin (acrylic acid-modified epoxy resin-2) comprises the following steps:

[0135] In a clean and dry 500ml four-necked flask, add 100g E-51 epoxy resin and 60.5g mixed solvent of xylene / n-butanol (the mass ratio of xylene to n-butanol is 6:4), mix all the materials evenly under stirring conditions and heat to 90°C, maintain this temperature, mix 38.5g acrylic acid, 3g N,N-dimethylaniline, 0.3g hydroquinone and 3g xylene evenly in advance for use, then slowly add the mixture dropwise from a constant pressure dropping funnel and finish dropping within 0.5h; after finishing dropping, slowly heat to 100°C and keep warm for 3h, then cool down to terminate the reaction, and after cooling the product, transfer it into a brown bottle to obtain acrylic acid-modified epoxy resin-2.

[0136] Example 3

[0137] A method for preparing an acrylic acid-modified epoxy resin (acrylic acid-modified epoxy resin-3) comprises the following steps:

[0138] In a clean and dry 500ml four-necked flask, add 100g E-51 epoxy resin and 60.5g mixed solvent of xylene / n-butanol (the mass ratio of xylene to n-butanol is 6:4), mix all the materials evenly under stirring conditions and heat to 90°C, maintain this temperature, mix 40.5g acrylic acid, 3g N,N-dimethylaniline, 0.3g hydroquinone and 3g xylene evenly in advance for use, then slowly add the mixture dropwise from a constant pressure dropping funnel and finish dropping within 0.5h; after finishing dropping, slowly heat to 110°C and keep warm for 3h, then cool down to terminate the reaction, and after cooling the product, transfer it into a brown bottle to obtain acrylic modified epoxy resin-3.

[0139] Some of the reaction conditions of Examples 1 to 3 and the properties of the products prepared are shown in Table 1 below.

[0140] Table 1

[0141]

[0142] Determination of viscosity of synthetic products:

[0143] The viscosity was measured using a TVB-10MW rotational viscometer produced by TOKI SANGYO of Japan; the measuring temperature was 30°C.

[0144] Test of acrylic acid conversion rate:

[0145] The conversion rate of the synthesis is determined by measuring the acid value. The acid value of the reaction system during the reaction and the acid value of the final product are determined by KOH-ethanol solution titration. The specific method is: weigh about 1g of sample, place it in a 250ml conical flask, dissolve the sample completely with 20ml acetone, add 3 drops of phenolphthalein indicator, and titrate with 0.1mol / L KOH-ethanol solution until pink is the end point. The calculation formula of the acid value is:

[0146]

[0147] Where: C is the concentration of KOH-ethanol solution (mol / L); V and V 0 are the volumes of KOH-ethanol solution consumed in titration and blank test respectively (ml); m is the mass of the sample (g); and 56.1 is the molar mass of KOH (g / mol).

[0148] The calculation formula of acrylic acid conversion is:

[0149] P=1-I / I 0

[0150] In the formula, P is the conversion rate of acrylic acid; I is the acid value of the product; I 0 is the initial acid value of the system.

[0151] The initial acid value calculation formula is:

[0152]

[0153] Embodiment 4-9

[0154] The preparation method of thermoplastic acrylate comprises the following steps:

[0155] In a four-necked flask equipped with a thermometer, a cooling tube, a stirrer, a dropping funnel, a nitrogen inlet tube and a temperature controller, xylene as a solvent was added, and the temperature was maintained at 110° C. Then, a mixed solution consisting of all the monomer materials in Table 2 and tert-butyl peroxy-2-ethylhexanoate as a free radical polymerization initiator was added to the dropping funnel, and the mixture was dropped into the four-necked flask at a constant rate for 3 hours, and the temperature was kept for 30 minutes after the dropping was completed; thus, a thermoplastic acrylate was obtained;

[0156] Wherein, in the above preparation method, the content of solvent xylene is 50wt% of the total mass of all raw materials, the content of initiator is 2wt% of the total mass of all raw materials, and the remainder is monomer material.

[0157] Table 2

[0158]

[0159] Examples 10-19

[0160] The preparation of the anti-corrosion coating having both anti-corrosion and transition connection functions comprises the following steps:

[0161] Preparation of component A:

[0162] According to the coating preparation method, the base resin, the first solvent, the adhesion promoter, and the pigment and filler in Table 3 were weighed in sequence. After high-speed dispersion for 0.5 h, the rheological additive was added, and the dispersion was performed again for 0.5 h until the fineness was less than 60 μm, and the component A of the coating was obtained by filtration;

[0163] Preparation of component B:

[0164] The amine curing agent, the second solvent and the curing accelerator are weighed in sequence and mixed to obtain component B of the coating.

[0165] Application of this anti-corrosion coating:

[0166] When in use, component A and component B are mixed evenly in a weight ratio of 100:(5-15). During the applicable period, the product is applied by spraying on the parts of marine engineering equipment and marine facilities that need to be protected from fouling, and is used in conjunction with antifouling coatings.

[0167] Table 3

[0168]

[0169]

[0170] Comparative Example 1-Comparative Example 5

[0171] An anti-corrosion coating, the formula of which is shown in Table 4 below, and the preparation method thereof is the same as that of the above-mentioned Examples 10-19.

[0172] Table 4

[0173]

[0174] In Table 3 and Table 4 above, the amine curing agent in component B belongs to a modified polyamide curing agent, specifically:

[0175] Amine curing agent 1: "ANCAMIDE 2050" manufactured by Air Products and Chemicals, Inc., an adduct of aliphatic polyamide modified with dimer acid and epoxy resin, amine value: 210 to 230 mgKOH / g.

[0176] Amine curing agent 2: "SUNMIDE 308D-65T" manufactured by Air Products and Chemicals, Inc., a dimer acid-modified aliphatic polyamide (amine component: pentaethylenehexamine), amine value: 180-200 mgKOH / g, non-volatile content: 65 wt%.

[0177] Amine curing agent 3: "SUNMIDE 305-70X" manufactured by Air Products and Chemicals, Inc., a dimer acid-modified aliphatic polyamide, amine value: 165-185 mgKOH / g, non-volatile content: 70 wt%.

[0178] 4266 is ALLNEX epoxy acrylate resin with a viscosity of 6500 mPas (23°C) and a Tg of 15°C.

[0179] is a solid thermoplastic acrylic copolymer from Covestro, with a Tg of 63°C and a weight average molecular weight Mw of 55,000. It is a thermoplastic acrylic copolymer with a solid content of 100%. The solid content of the thermoplastic acrylic resin used in Examples 10-18 is 50%.

[0180] Sample preparation:

[0181] The cold-rolled steel plate was sandblasted (70*150*2mm), coated with inorganic zinc shop primer (trade name "NIPPONCERAMO"), with a dry film thickness of 15μm, and dried at room temperature for 7 days before being used as a test substrate; the above-mentioned anti-corrosion coating was sprayed using air, with a dry film thickness of about 250μm, and after drying for one day, the anti-corrosion epoxy coating was sprayed again, with a dry film thickness of about 75μm, thereby obtaining a test plate.

[0182] Anti-corrosion performance test:

[0183] After the above test panels have been dried for 7 days, the artificial seawater immersion resistance test is carried out according to GB / T 10834, 40°C / 6M; the condensation chamber test is carried out according to GB / T 6823, the time is 6M.

[0184] The evaluation method is to observe whether there are defects on the coating surface, and then use the Elcometer pull-off instrument to test the adhesion (MPa) after aging.

[0185] Adhesion test with antifouling topcoat:

[0186] The test plate was exposed to the outdoors, and after 1 day, an antifouling topcoat (Ecoloflex SPC series, A-LF-Sea series) was sprayed on the test plate, and the dry film thickness was about 150 μm, and the test plate was dried indoors for 24 hours; then, the test plate was immersed in artificial seawater for 6 months, and immediately after being taken out, a cross-cut method based on JIS K 5600-5-6 was performed with a gap interval of 5 mm and a grid number of 9 to evaluate the topcoat adhesion. The evaluation criteria are as follows, and the evaluation result is preferably 3 or more:

[0187] 5: The peeling area of ​​the cut part is less than 5%;

[0188] 4: The peeling area of ​​the cut part is greater than 5% and less than 15%;

[0189] 3: The peeling area of ​​the cut part is greater than 15% and less than 35%;

[0190] 2: The peeling area of ​​the cut part is greater than 35% and less than 65%;

[0191] 1: The peeling area of ​​the cut portion is greater than 65% and less than 100%.

[0192] The properties of the coatings formed in the above examples or comparative examples are shown in Tables 5 and 6 below.

[0193] Table 5

[0194]

[0195] Table 6

[0196]

[0197]

[0198] Obviously, the above embodiments of the present invention are merely examples for clearly illustrating the present invention, and are not limitations on the implementation methods of the present invention. For ordinary technicians in the relevant field, other different forms of changes or modifications can be made based on the above description. It is impossible to list all the implementation methods here. All obvious changes or modifications derived from the technical solution of the present invention are still within the protection scope of the present invention.

Claims

1. An anti-corrosion coating, characterized in that: The anticorrosive coating is composed of component A and component B in a weight ratio of 100:(5-15); wherein, The component A comprises the following components by weight percentage: 30-45% base resin, 0.3-1% adhesion promoter, 0.1-1% rheological additive, 40-55% pigment and filler, and 10-25% first solvent; The matrix resin is a mixture of acrylic modified epoxy resin, thermoplastic acrylic resin and first epoxy resin; Wherein, the acrylic modified epoxy resin is prepared by esterification reaction of a second epoxy resin with acrylic acid or methacrylic acid; The component B comprises the following components by weight percentage: 65-75% of amine curing agent, 1-3% of curing accelerator and 23-33% of second solvent.

2. The anticorrosive coating according to claim 1, characterized in that: The mass ratio of the first epoxy resin, the thermoplastic acrylic resin and the acrylic modified epoxy resin is 100:(30-70):(10-30), preferably 100:(40-70):(10-30), and more preferably 100:(45-65):(15-25).

3. The anticorrosive coating according to claim 1, characterized in that: During the preparation of the acrylic modified epoxy resin, the molar ratio of the second epoxy resin to acrylic acid or methacrylic acid is 1:1 to 1:3, preferably 1:1.9 to 1:2.1; Preferably, the temperature of the esterification reaction is 80 to 120° C., more preferably 90 to 110° C., and the time of the esterification reaction is 2 to 6 hours, preferably 4 hours.

4. The anticorrosive coating according to claim 1, characterized in that: The solubility parameter of the first epoxy resin is 10.2 to 12, preferably 10.5 to 11.5; the weight average molecular weight is 250 to 2500 g / mol, preferably 350 to 1500 g / mol; the epoxy equivalent is 100 to 3000 g / equivalent, preferably 150 to 1000 g / equivalent; Preferably, the first epoxy resin is selected from one or more of bisphenol A epoxy resin, bisphenol F epoxy resin, bisphenol AD ​​epoxy resin, bisphenol S epoxy resin, biphenyl epoxy resin and rubber modified epoxy resin.

5. The anticorrosive coating according to claim 1, characterized in that: The solubility parameter of the thermoplastic acrylic resin is 9.2 to 12, preferably 9.6 to 11.5; the glass transition temperature is 40 to 90° C., preferably 60 to 72° C.; the weight average molecular weight is 1000 to 90000 g / mol, preferably 1000 to 60000 g / mol; Preferably, the absolute value of the difference between the solubility parameters of the thermoplastic acrylic resin and the first epoxy resin is less than 2.

5.

6. The anticorrosive coating according to claim 5, characterized in that: The thermoplastic acrylic resin is a (meth)acrylic acid homopolymer or (meth)acrylic acid copolymer containing a structural unit derived from (meth)acrylic acid ester; Preferably, the thermoplastic acrylic resin is obtained by free radical polymerization of acrylic monomers, the polymerization temperature of the free radical polymerization is 90 to 110° C., and the polymerization time is 3 to 8 hours; Preferably, the acrylic monomer is selected from one or more of n-butyl acrylate, methyl methacrylate, styrene, ethyl acrylate, n-butyl methacrylate, 2-ethylhexyl methacrylate, 2-hydroxyethyl methacrylate and hydroxyethyl acrylate.

7. The anticorrosive coating according to claim 1, characterized in that: In the component B, the amine curing agent is compounded by a modified polyamide curing agent having an amine value of 210-230 mgKOH / g and a modified polyamide curing agent having an amine value of 160-200 mgKOH / g; Preferably, the modified polyamide curing agent with an amine value of 210-230 mgKOH / g is an adduct of an aliphatic polyamide modified by dimer acid and an epoxy resin; Preferably, the modified polyamide curing agent having an amine value of 160-200 mgKOH / g is a dimer acid-modified aliphatic polyamide; Preferably, the mixing ratio of the modified polyamide curing agent having an amine value of 210-230 mgKOH / g and the modified polyamide curing agent having an amine value of 160-200 mgKOH / g is 1:(0.5-1.5).

8. The method for preparing the anticorrosive coating according to any one of claims 1 to 7, characterized in that: The steps include: The preparation of component A comprises the following steps: The base resin, the first solvent, the adhesion promoter, and the pigment are mixed, and then the rheological additive is added, mixed and dispersed to a fineness of less than 60 μm to obtain the component A; The preparation of component B comprises the following steps: The amine curing agent, the curing accelerator and the second solvent are mixed to obtain the component B.

9. Use of the anti-corrosion coating according to any one of claims 1 to 7 in the protection of marine engineering equipment or marine facilities.

10. The use according to claim 9, characterized in that: Applying the anti-corrosion coating on the marine engineering equipment or marine facilities; Preferably, the coating of the marine engineering equipment or marine facilities includes: The anti-corrosion coating and anti-fouling coating are sequentially applied to the parts of the marine engineering equipment or marine facilities that need to be painted or protected from fouling.

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