CN114181582A - Nontoxic efficient porphyrin derivative modified acrylic resin water-based anticorrosive paint - Google Patents
Nontoxic efficient porphyrin derivative modified acrylic resin water-based anticorrosive paint Download PDFInfo
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- CN114181582A CN114181582A CN202111511795.9A CN202111511795A CN114181582A CN 114181582 A CN114181582 A CN 114181582A CN 202111511795 A CN202111511795 A CN 202111511795A CN 114181582 A CN114181582 A CN 114181582A
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
- C09D133/04—Homopolymers or copolymers of esters
- C09D133/14—Homopolymers or copolymers of esters of esters containing halogen, nitrogen, sulfur or oxygen atoms in addition to the carboxy oxygen
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
- C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
- C08F220/1812—C12-(meth)acrylate, e.g. lauryl (meth)acrylate
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
- C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
- C08F220/1818—C13or longer chain (meth)acrylate, e.g. stearyl (meth)acrylate
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/08—Anti-corrosive paints
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/14—Paints containing biocides, e.g. fungicides, insecticides or pesticides
Abstract
The invention relates to a nontoxic efficient porphyrin derivative modified acrylic resin water-based anticorrosive coating which comprises the following components in parts by weight: 50.0-100.0 parts of porphyrin derivative modified water-based acrylic resin, 0.3-0.8 part of wetting agent, 0.4-1.0 part of dispersing agent, 0.3-0.8 part of defoaming agent, 0.3-0.6 part of flatting agent, 0.5-1.0 part of pH regulator, 3.5-6.5 parts of methyl potassium silicate, 0.5-1.5 parts of hydroxy cellulose, 5.0-12.0 parts of silica type transparent powder, 10.0-30.0 parts of pigment and filler and 15.0-45.0 parts of distilled water; the nontoxic efficient porphyrin derivative modified acrylic resin water-based anticorrosive coating prepared by the invention does not need additional bactericide and anticorrosive auxiliary agent, and has good antibacterial property and anticorrosive property; film forming additives are not needed, and the film forming performance is good, the fullness is good, and the adhesive force is strong; and the paint has the characteristics of low surface tension of a paint film, difficulty in covering the surface with pollutants and the like.
Description
Technical Field
The invention relates to a modified acrylic resin water-based paint, in particular to a nontoxic efficient porphyrin derivative modified acrylic resin water-based anticorrosive paint, belonging to the technical field of water-based functional paints.
Background
Objects exposed in the atmospheric environment are corroded by various corrosion factors, the inner walls of containers contacting various corrosive media, sewage treatment pools, harbor facilities and the like are in a corrosion state all the year round, all products and equipment are often subjected to various mechanical impacts, scratches, scouring of violent wind and storm rain, corrosion of wind and sand and the like, and corrosion protection is needed.
Paint is one of the widely used methods for preventing and controlling corrosion, and different coating materials and processes are applicable to different fields. From a long term and application scale, the coating plays a remarkable role in the aspects of reducing maintenance cost, preventing corrosion, improving equipment safety and the like, and the cost performance of the coating protection mode is higher. At present, most of traditional heavy anti-corrosion coatings applied to marine environments are scale filler type anti-corrosion coatings which are distributed in a coating layer in an overlapping mode to generate a labyrinth effect and prolong a corrosion medium diffusion path. However, when the filler content is too high, the bonding property of the coating and the matrix is poor, and the coating is easy to crack when the film layer is too thick, so that the shielding property of the coating is poor, and the corrosion-resistant service life in a heavily polluted or severe marine environment is seriously insufficient. Furthermore, traditionally effective antifouling coatings in preventing marine biofouling organisms from attaching are coatings containing TBT biocides, however such coatings also have a biocidal effect on non-target organisms. The polishing type copper oxide or zinc oxide antifouling paint is the mainstream of the prior art, and although the polishing type copper oxide or zinc oxide antifouling paint meets the current environmental protection requirement, a large amount of copper and zinc elements are accumulated in the ocean, so that a large amount of marine organisms are killed, and the ecological balance is damaged.
Because of the special light, heat and chemical stability of the C-C main chain and the modifiability of groups on the side chain, the acrylic resin has unique advantages in the aspects of weather resistance, oil resistance, solvent resistance and the like in the acrylic coating serving as a main film forming base material, and is widely favored in the fields of industry and civil buildings. However, the traditional acrylic resin used for the metal anticorrosive paint has certain defects. Firstly, the coating based on the traditional solvent type acrylic resin needs a large amount of organic solvent for dilution due to the large molecular weight and high viscosity of the resin, which is not beneficial to environmental protection and has low coating efficiency. Secondly, the coating is easy to generate flash corrosion, once flash corrosion points occur, the integrity of the paint film is damaged, and the rust-proof and corrosion-proof functions of the paint film are greatly reduced.
Chinese patent CN102816481A discloses an anticorrosive paint based on aminated linoleic acid copolymerized acrylic resin and a preparation method thereof, wherein the paint comprises the following components: aminated linoleic acid copolymerized acrylic resin, micaceous iron oxide, zinc phosphate, aluminum tripolyphosphate, mica powder, talcum powder, organic bentonite, butyl acetate, ethyl acetate and the like; chinese patent CN110819193A discloses a self-flame-retardant acrylic resin water-based anticorrosive paint, which comprises the following components in parts by weight: 100.0-150.0 parts of self-flame-retardant oleyl polyether-2 phosphate modified water-based acrylic anticorrosive resin, 20.0-40.0 parts of fluorine modified water-based acrylic resin, 0.2-0.6 part of wetting agent, 0.2-0.5 part of defoaming agent, 0.2-0.8 part of thickening and leveling agent, 0.3-0.7 part of pH regulator, 6.0-10.0 parts of antifreezing agent and 10.0-25.0 parts of deionized water; the above patents all contain a large amount of phosphorus element.
Chinese patent CN112239625A discloses a silica-graphene oxide/polyurethane acrylic resin anticorrosion coating, which is characterized in that it comprises the following preparation steps: (1) firstly, the range of a graphene oxide raw material is from several micrometers to dozens of micrometers; (2) secondly, preparing the silane coupling agent modified graphene oxide, wherein the silane coupling agent modified graphene oxide can be obtained under different reaction conditions; (3) in the third step, the nano-scale silicon dioxide can be directly utilized and then the silane coupling agent is loaded on the modified graphene oxide. The prepared graphene water-based anti-corrosion coating can effectively solve the problem of poor anti-corrosion performance of a water-based paint; the invention mainly solves the problem of electrochemical corrosion by using graphene.
Therefore, the development of a nontoxic and effective anticorrosive coating meets the requirement of social development.
Disclosure of Invention
In order to solve the technical problems existing at present, the invention aims to provide a nontoxic efficient porphyrin derivative modified acrylic resin water-based anticorrosive paint.
The invention takes porphyrin derivative modified water-based acrylic resin as a main film forming substance, the porphyrin derivative modified water-based acrylic resin is formed by connecting porphyrin derivative and water-based acrylic resin through chemical bonds, the performance is stable and durable, and the porphyrin derivative modified water-based acrylic resin is not easy to separate, porphyrin can form a complex with metal ions, the metal ions on the metal surface can be protected, and a coating forms a compact protective film; the film forming assistant is not needed, and the fullness is good.
The invention relates to a nontoxic efficient porphyrin derivative modified acrylic resin water-based anticorrosive coating which comprises the following components in parts by weight: 50.0-100.0 parts of porphyrin derivative modified water-based acrylic resin, 0.3-0.8 part of wetting agent, 0.4-1.0 part of dispersing agent, 0.3-0.8 part of defoaming agent, 0.3-0.6 part of flatting agent, 0.5-1.0 part of pH regulator, 3.5-6.5 parts of methyl potassium silicate, 0.5-1.5 parts of hydroxy cellulose, 5.0-12.0 parts of silica type transparent powder, 10.0-30.0 parts of pigment and filler and 15.0-45.0 parts of distilled water.
The pH regulator is one or a combination of more of AMP-95, sodium bicarbonate, sodium carbonate, ammonia water and triethylamine.
The pigment and filler is one or a combination of more of mica powder, barium sulfate, kaolin, calcium carbonate, bentonite and water-based color paste.
The porphyrin derivative modified waterborne acrylic resin comprises the following components in parts by weight: 5.0-8.0 parts of porphyrin derivative, 20.0-40.0 parts of diisocyanate, 3.5-8.0 parts of dimethylolpropionic acid, 2.0-4.0 parts of absolute ethyl alcohol, 0.01-0.05 part of dibutyltin dilaurate, 2.5-4.5 parts of crosslinking monomer, 0.2-0.6 part of ammonium persulfate, 3.0-6.0 parts of trimethylolpropane trimethacrylate, 10.0-30.0 parts of hard acrylate monomer, 25.0-60.0 parts of soft acrylate monomer, 8.0-15.0 parts of film-forming assistant, 2.5-7.5 parts of neutralizer and 100.0-220.0 parts of deionized water; the porphyrin derivative containing hydroxyl is prepared by pyrrole, hydroxycitronellal and benzaldehyde through chemical reaction.
The diisocyanate is one or a combination of toluene diisocyanate, isophorone diisocyanate and hexamethylene diisocyanate.
The acrylate hard monomer is one or a combination of methyl acrylate, methyl methacrylate, acrylamide, isobornyl acrylate and cyclohexyl methacrylate.
The acrylate soft monomer is one or a combination of butyl methacrylate, isooctyl methacrylate, lauryl methacrylate, tridecyl methacrylate and stearyl acrylate.
The crosslinking monomer is one or a combination of more of hydroxypropyl acrylate, hydroxyethyl propionate and hydroxybutyl acrylate.
The film-forming additive is one or a combination of a plurality of alcohol ester dodeca, propylene glycol phenyl ether, cetyl alcohol ester, dipropylene glycol butyl ether and propylene glycol methyl ether acetate.
The neutralizing agent is one or the combination of triethylamine and ammonia water.
The preparation method of the porphyrin derivative modified waterborne acrylic resin comprises the following steps:
a. preparing 5% ammonium persulfate aqueous solution by weight parts of ammonium persulfate;
b. in a titration tank, uniformly stirring an acrylate hard monomer, an acrylate soft monomer and trimethylolpropane trimethacrylate according to the weight part of the formula to obtain a mixed solution I;
c. sequentially adding dimethylolpropionic acid, diisocyanate and 1/3 mixed solution I according to the weight part of the formula into a multifunctional reaction kettle, heating to 78-80 ℃, stirring and reacting for 2h, then adding dibutyltin dilaurate according to the formula amount, controlling the temperature to be 80-82 ℃, simultaneously adding porphyrin derivative and crosslinking monomer, stirring and reacting for 2.0h, and measuring the NCO value until the NCO value is consistent with the designed value;
d. adding absolute ethyl alcohol, stirring and reacting for 1h, cooling, adding a neutralizing agent, adding deionized water, and uniformly dispersing to obtain an aqueous dispersion;
e) and introducing nitrogen into the reactor, adding the aqueous dispersion, the film-forming assistant and 1/3 ammonium persulfate aqueous solution, uniformly stirring, heating to 80-82 ℃, simultaneously dropwise adding the rest of mixed solution I and the rest of ammonium persulfate aqueous solution, finishing dropwise adding for 3.0-3.5 h, heating to 86-88 ℃ after completing dropwise adding, carrying out heat preservation reaction for 2.0h, and filtering to obtain the porphyrin derivative modified aqueous acrylic resin.
The porphyrin derivative modified waterborne acrylic resin is based on the applied invention patent of 'a porphyrin derivative modified waterborne acrylic resin and a preparation method thereof', and is described in detail.
The nontoxic efficient porphyrin derivative modified acrylic resin water-based anticorrosive coating prepared by the invention does not need additional bactericide and anticorrosive auxiliary agent, and has good antibacterial property and anticorrosive property; when the system coating is prepared, no film-forming auxiliary agent is required to be added, so that the film-forming property is good, the fullness is good, the flexibility is good, and the adhesive force is strong; the nontoxic efficient porphyrin derivative modified acrylic resin water-based anticorrosive coating prepared by the invention has the characteristics of low surface tension of a paint film, difficulty in covering the surface with pollutants and the like.
Detailed Description
The invention is further described by combining the following examples with a nontoxic efficient porphyrin derivative modified acrylic resin waterborne anticorrosive coating. It is to be understood that the specific embodiments described herein are merely illustrative of the relevant invention and not restrictive of the invention.
In the present invention, all parts and percentages are by weight, unless otherwise specified, and the equipment and materials used are commercially available or commonly used in the art. The methods in the following examples are conventional in the art unless otherwise specified.
Example 1
A porphyrin derivative modified waterborne acrylic resin X comprises the following components in parts by weight: 7.0 parts of porphyrin derivative, 36.0 parts of isophorone diisocyanate, 6.8 parts of dimethylolpropionic acid, 3.5 parts of absolute ethyl alcohol, 0.04 part of dibutyltin dilaurate, 3.0 parts of hydroxyethyl propionate, 0.5 part of ammonium persulfate, 6.0 parts of trimethylolpropane trimethacrylate, 22.0 parts of isobornyl acrylate, 50.0 parts of lauryl methacrylate, 13.0 parts of hexadecanol ester, 6.5 parts of triethylamine and 200.0 parts of deionized water.
The preparation method of the porphyrin derivative modified waterborne acrylic resin X in the embodiment comprises the following steps:
a. preparing 5% ammonium persulfate aqueous solution by weight parts of ammonium persulfate;
b. in a titration tank, uniformly stirring isobornyl acrylate, lauryl methacrylate and trimethylolpropane trimethacrylate in parts by weight of a formula to obtain a mixed solution I;
c. sequentially adding a mixed solution I of dimethylolpropionic acid, isophorone diisocyanate and 1/3 in parts by weight of a formula into a multifunctional reaction kettle, heating to 78-80 ℃, stirring for reaction for 2 hours, then adding dibutyltin dilaurate in the formula amount, controlling the temperature to be 80-82 ℃, simultaneously adding a porphyrin derivative and hydroxyethyl propionate, stirring for reaction for 2.0 hours, and measuring an NCO value until the NCO value is consistent with a designed value;
d. adding absolute ethyl alcohol, stirring and reacting for 1h, cooling, adding triethylamine, adding deionized water, and dispersing uniformly to obtain an aqueous dispersion;
e) and introducing nitrogen into the reactor, adding the aqueous dispersion, the hexadecanol ester and the 1/3 ammonium persulfate aqueous solution, uniformly stirring, heating to 80-82 ℃, simultaneously dropwise adding the rest of the mixed solution I and the rest of the ammonium persulfate aqueous solution, finishing dropwise adding within 3.0-3.5 h, heating to 86-88 ℃ after completing dropwise adding, carrying out heat preservation reaction for 2.0h, and filtering to obtain the porphyrin derivative modified aqueous acrylic resin X.
Example 2
The porphyrin derivative modified waterborne acrylic resin Y comprises the following components in parts by weight: 6.0 parts of porphyrin derivative, 25.0 parts of hexamethylene diisocyanate, 5.0 parts of dimethylolpropionic acid, 4.0 parts of absolute ethyl alcohol, 0.05 part of dibutyltin dilaurate, 4.0 parts of hydroxybutyl acrylate, 0.5 part of ammonium persulfate, 5.0 parts of trimethylolpropane trimethacrylate, 20.0 parts of cyclohexyl methacrylate, 55.0 parts of tridecyl methacrylate, 5.5 parts of dipropylene glycol butyl ether, 5.5 parts of propylene glycol methyl ether acetate, 4.0 parts of ammonia water and 175.0 parts of deionized water.
The preparation method of the porphyrin derivative modified waterborne acrylic resin Y in the embodiment comprises the following steps:
a. preparing 5% ammonium persulfate aqueous solution by weight parts of ammonium persulfate;
b. in a titration tank, uniformly stirring cyclohexyl methacrylate, tridecyl methacrylate and trimethylolpropane trimethacrylate according to the weight part of the formula to obtain a mixed solution I;
c. sequentially adding a mixed solution I of dimethylolpropionic acid, hexamethylene diisocyanate and 1/3 in parts by weight into a multifunctional reaction kettle, heating to 78-80 ℃, stirring and reacting for 2 hours, then adding dibutyltin dilaurate in a formula amount, controlling the temperature to be 80-82 ℃, simultaneously adding a porphyrin derivative and hydroxybutyl acrylate, stirring and reacting for 2.0 hours, and measuring an NCO value until the NCO value is consistent with a designed value;
d. adding absolute ethyl alcohol, stirring and reacting for 1h, cooling, adding ammonia water, adding deionized water, and dispersing uniformly to obtain an aqueous dispersion;
e) and introducing nitrogen into the reactor, adding the aqueous dispersion, dipropylene glycol butyl ether, propylene glycol methyl ether acetate and 1/3 ammonium persulfate aqueous solution, uniformly stirring, heating to 80-82 ℃, simultaneously dropwise adding the rest of mixed solution I and the rest of ammonium persulfate aqueous solution, finishing dropwise adding for 3.0-3.5 h, heating to 86-88 ℃ after completing dropwise adding, carrying out heat preservation reaction for 2.0h, and filtering to obtain the porphyrin derivative modified aqueous acrylic resin Y.
Comparative example 1
A conventional modified waterborne acrylic resin A comprises the following components in parts by weight: 29.0 parts of isophorone diisocyanate, 6.0 parts of dimethylolpropionic acid, 3.0 parts of absolute ethyl alcohol, 0.04 part of dibutyltin dilaurate, 3.5 parts of hydroxyethyl propionate, 0.4 part of ammonium persulfate, 6.0 parts of trimethylolpropane trimethacrylate, 15.0 parts of methyl methacrylate, 45.0 parts of octadecyl acrylate, 12.0 parts of alcohol ester twelve, 4.5 parts of ammonia water and 165.0 parts of deionized water.
The preparation method of the conventional modified waterborne acrylic resin A in the embodiment comprises the following steps:
a. preparing 5% ammonium persulfate aqueous solution by weight parts of ammonium persulfate;
b. uniformly stirring methyl methacrylate, octadecyl acrylate and trimethylolpropane trimethacrylate in parts by weight of a formula in a titration tank to obtain a mixed solution I;
c. sequentially adding a mixed solution I of dimethylolpropionic acid, isophorone diisocyanate and 1/3 in parts by weight of a formula into a multifunctional reaction kettle, heating to 78-80 ℃, stirring for reaction for 2 hours, then adding dibutyltin dilaurate in the formula amount, controlling the temperature to be 80-82 ℃, adding hydroxyethyl propionate, stirring for reaction for 2.0 hours, and measuring an NCO value until the NCO value is consistent with a designed value;
d. adding absolute ethyl alcohol, stirring and reacting for 1h, cooling, adding ammonia water, adding deionized water, and dispersing uniformly to obtain an aqueous dispersion;
e) and introducing nitrogen into the reactor, adding the aqueous dispersion, alcohol ester dodeca and 1/3 ammonium persulfate aqueous solution, uniformly stirring, heating to 80-82 ℃, simultaneously dropwise adding the rest of mixed solution I and the rest of ammonium persulfate aqueous solution, finishing dropwise adding for 3.0-3.5 h, heating to 86-88 ℃ after completing dropwise adding, carrying out heat preservation reaction for 2.0h, and filtering to obtain the conventional modified aqueous acrylic resin A.
Example 3
A nontoxic efficient porphyrin derivative modified acrylic resin water-based anticorrosive coating comprises the following components in parts by weight: 80.0 parts of porphyrin derivative modified waterborne acrylic resin X, 0.8 part of wetting agent, 0.6 part of dispersing agent, 0.5 part of defoaming agent, 0.3 part of flatting agent, AMP-950.7 part, 4.5 parts of methyl potassium silicate, 1.0 part of hydroxy cellulose, 8.0 parts of silica type transparent powder, 10.0 parts of kaolin, 10.0 parts of calcium carbonate and 30.0 parts of distilled water.
Example 4
A nontoxic efficient porphyrin derivative modified acrylic resin water-based anticorrosive coating comprises the following components in parts by weight: 70.0 parts of porphyrin derivative modified waterborne acrylic resin Y, 0.4 part of wetting agent, 0.8 part of dispersing agent, 0.7 part of defoaming agent, 0.5 part of flatting agent, 0.8 part of sodium bicarbonate, 6.5 parts of methyl potassium silicate, 1.2 parts of hydroxy cellulose, 12.0 parts of silica type transparent powder, 15.0 parts of mica powder, 10.0 parts of barium sulfate and 40.0 parts of distilled water.
Comparative example 2
A conventional modified acrylic resin waterborne anticorrosive coating comprises the following components in parts by weight: 70.0 parts of conventional modified water-based acrylic resin A, 0.5 part of wetting agent, 0.8 part of dispersing agent, 0.6 part of defoaming agent, 0.5 part of flatting agent, 4.5 parts of methyl potassium silicate, 0.7 part of triethylamine, 0.5 part of hydroxy cellulose, 5.0 parts of silicon dioxide type transparent powder, 8.0 parts of bentonite, 15.0 parts of water-based color paste and 20.0 parts of distilled water.
The performance index test was performed on inventive examples 3 and 4 and comparative example 2 according to the relevant standards, and the test results are shown in table 1.
Wherein, filiform corrosion: detecting according to the regulation of (GB/T13452.4-92);
hardness: measuring the hardness of the paint film according to GB/T6739-2006 color paint and a pencil cleaning method;
contact angle: detecting according to the regulation of GB/T30693-2014;
acid mist resistance: detecting according to the regulation of GB/T9274;
and (3) antibacterial property: the detection is carried out according to the regulation of HG/T3950-2007 antimicrobial paint.
Table 1: performance specification of coating
| Detecting items | Example 3 | Coating 4 | Comparative example 2 |
| Acid mist resistance/480 h | Normal paint film | Normal paint film | Discoloration of paint film |
| Hardness of | H | H | HB |
| Fullness (visual inspection) | Good effect | Good effect | In general |
| Filiform corrosion | Light and slight | Light and slight | Severe severity of disease |
| Contact angle | 126° | 118° | 72° |
| Antibacterial property (Staphylococcus aureus) | 99.72％ | 99.68％ | 58.92％ |
It can be seen from table 1 that the filiform corrosion, antibacterial property (staphylococcus aureus), acid fog resistance and other properties of the samples of example 3 and example 4 of the invention are far better than those of the conventional modified acrylic resin water-based anticorrosive paint (comparative example 1), which indicates that the filiform corrosion, acid fog resistance and other properties of a paint film can be effectively improved due to the addition of the porphyrin derivative modified water-based acrylic resin, and the nontoxic efficient porphyrin derivative modified acrylic resin water-based anticorrosive paint has good antibacterial property;
as can be seen from Table 1, the contact angles of the acrylic resin aqueous anticorrosive coatings prepared in the examples 3 and 4 and the comparative example 2 are larger than 90 degrees, which shows that the nontoxic efficient porphyrin derivative modified acrylic resin aqueous anticorrosive coatings prepared in the examples have low surface tension, good stain resistance and strong self-cleaning capability.
The foregoing description is only a preferred embodiment of the application and is illustrative of the principles of the technology employed; it will be appreciated by a person skilled in the art that the scope of the invention as referred to in the present application is not limited to the embodiments with a specific combination of the above-mentioned features, but also covers other embodiments with any combination of the above-mentioned features or their equivalents without departing from the inventive concept. For example, the above features may be replaced with (but not limited to) features having similar functions disclosed in the present application.
Claims (4)
1. A nontoxic efficient porphyrin derivative modified acrylic resin water-based anticorrosive paint is characterized in that: the composition comprises the following components in parts by weight: 50.0-100.0 parts of porphyrin derivative modified water-based acrylic resin, 0.3-0.8 part of wetting agent, 0.4-1.0 part of dispersing agent, 0.3-0.8 part of defoaming agent, 0.3-0.6 part of flatting agent, 0.5-1.0 part of pH regulator, 3.5-6.5 parts of methyl potassium silicate, 0.5-1.5 parts of hydroxy cellulose, 5.0-12.0 parts of silica type transparent powder, 10.0-30.0 parts of pigment and filler and 15.0-45.0 parts of distilled water; the preparation method of the porphyrin derivative modified waterborne acrylic resin comprises the following steps:
a. preparing 5% ammonium persulfate aqueous solution by weight parts of ammonium persulfate;
b. in a titration tank, uniformly stirring an acrylate hard monomer, an acrylate soft monomer and trimethylolpropane trimethacrylate according to the weight part of the formula to obtain a mixed solution I;
c. sequentially adding dimethylolpropionic acid, diisocyanate and 1/3 mixed solution I according to the weight part of the formula into a multifunctional reaction kettle, heating to 78-80 ℃, stirring and reacting for 2h, then adding dibutyltin dilaurate according to the formula amount, controlling the temperature to be 80-82 ℃, simultaneously adding porphyrin derivative and crosslinking monomer, stirring and reacting for 2.0h, and measuring the NCO value until the NCO value is consistent with the designed value;
d. adding absolute ethyl alcohol, stirring and reacting for 1h, cooling, adding a neutralizing agent, adding deionized water, and uniformly dispersing to obtain an aqueous dispersion;
e) and introducing nitrogen into the reactor, adding the aqueous dispersion, the film-forming assistant and 1/3 ammonium persulfate aqueous solution, uniformly stirring, heating to 80-82 ℃, simultaneously dropwise adding the rest of mixed solution I and the rest of ammonium persulfate aqueous solution, finishing dropwise adding for 3.0-3.5 h, heating to 86-88 ℃ after completing dropwise adding, carrying out heat preservation reaction for 2.0h, and filtering to obtain the porphyrin derivative modified aqueous acrylic resin.
2. The non-toxic high-efficiency porphyrin derivative modified acrylic resin water-based anticorrosive coating as claimed in claim 1, characterized in that: the porphyrin derivative modified waterborne acrylic resin comprises the following components in parts by weight: 5.0-8.0 parts of porphyrin derivative, 20.0-40.0 parts of diisocyanate, 3.5-8.0 parts of dimethylolpropionic acid, 2.0-4.0 parts of absolute ethyl alcohol, 0.01-0.05 part of dibutyltin dilaurate, 2.5-4.5 parts of crosslinking monomer, 0.2-0.6 part of ammonium persulfate, 3.0-6.0 parts of trimethylolpropane trimethacrylate, 10.0-30.0 parts of acrylate hard monomer, 25.0-60.0 parts of acrylate soft monomer, 8.0-15.0 parts of film-forming assistant, 2.5-7.5 parts of neutralizer and 100.0-220.0 parts of deionized water.
3. The non-toxic high-efficiency porphyrin derivative modified acrylic resin water-based anticorrosive coating as claimed in claim 1, characterized in that: the pH regulator is one or a combination of more of AMP-95, sodium bicarbonate, sodium carbonate, ammonia water and triethylamine.
4. The non-toxic high-efficiency porphyrin derivative modified acrylic resin water-based anticorrosive coating as claimed in claim 1, characterized in that: the pigment and filler is one or a combination of more of mica powder, barium sulfate, kaolin, calcium carbonate, bentonite and water-based color paste.
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| US5360880A (en) * | 1990-07-06 | 1994-11-01 | The Australian National University | Polymerizable porphyrins |
| WO1996001282A1 (en) * | 1994-07-01 | 1996-01-18 | Memtec Limited | Water-based porphyrin coating system |
| CN102838606A (en) * | 2012-09-18 | 2012-12-26 | 中国石油天然气股份有限公司 | Corrosion-inhibition drag reducer for alkyl porphyrin compound natural gas pipelines and preparation method of corrosion-inhibition drag reducer |
| CN110845931A (en) * | 2019-11-19 | 2020-02-28 | 合众（佛山）化工有限公司 | Polyether amine modified acrylic resin water-based anticorrosive paint and preparation method thereof |
| CN112143377A (en) * | 2020-08-14 | 2020-12-29 | 广西昌用电线电缆有限公司 | Corona-resistant coating for cable and preparation method thereof |
| CN112646084A (en) * | 2020-12-18 | 2021-04-13 | 合众（佛山）化工有限公司 | Tripolyindenone derivative modified waterborne acrylic resin and preparation method thereof |
-
2021
- 2021-12-06 CN CN202111511795.9A patent/CN114181582A/en not_active Withdrawn
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5360880A (en) * | 1990-07-06 | 1994-11-01 | The Australian National University | Polymerizable porphyrins |
| WO1996001282A1 (en) * | 1994-07-01 | 1996-01-18 | Memtec Limited | Water-based porphyrin coating system |
| CN102838606A (en) * | 2012-09-18 | 2012-12-26 | 中国石油天然气股份有限公司 | Corrosion-inhibition drag reducer for alkyl porphyrin compound natural gas pipelines and preparation method of corrosion-inhibition drag reducer |
| CN110845931A (en) * | 2019-11-19 | 2020-02-28 | 合众（佛山）化工有限公司 | Polyether amine modified acrylic resin water-based anticorrosive paint and preparation method thereof |
| CN112143377A (en) * | 2020-08-14 | 2020-12-29 | 广西昌用电线电缆有限公司 | Corona-resistant coating for cable and preparation method thereof |
| CN112646084A (en) * | 2020-12-18 | 2021-04-13 | 合众（佛山）化工有限公司 | Tripolyindenone derivative modified waterborne acrylic resin and preparation method thereof |
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