CN115124906A - Underwater construction curing coating and preparation method and application thereof - Google Patents
Underwater construction curing coating and preparation method and application thereof Download PDFInfo
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- CN115124906A CN115124906A CN202210909146.2A CN202210909146A CN115124906A CN 115124906 A CN115124906 A CN 115124906A CN 202210909146 A CN202210909146 A CN 202210909146A CN 115124906 A CN115124906 A CN 115124906A
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- 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
- C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/44—Amides
- C08G59/46—Amides together with other curing agents
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
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- C08G59/5026—Amines cycloaliphatic
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- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/50—Amines
- C08G59/5033—Amines aromatic
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/50—Amines
- C08G59/56—Amines together with other curing agents
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/62—Alcohols or phenols
- C08G59/621—Phenols
- C08G59/623—Aminophenols
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- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/66—Mercaptans
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- 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
- C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
- C09D163/04—Epoxynovolacs
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Abstract
The invention discloses an underwater construction curing coating and a preparation method and application thereof, belonging to the technical field of underwater protective coatings. The underwater construction curing coating comprises a component A and a component B; the component A comprises the following components in parts by weight: 30-50 parts of epoxy resin; 5-10 parts of a reactive solvent; 3-10 parts of a hydrophobic modifier; 30-60 parts of pigment and filler; 2-7 parts of an auxiliary agent; the component B comprises the following components in parts by weight: 40-80 parts of hyperbranched polythiol; 16-57 parts of an amine curing agent; 2-10 parts of an accelerator. The underwater construction curing coating developed by the invention has the characteristics of high hydrophobicity, quick curing and high adhesive force, can be effectively coated and cured underwater, and can be applied to the fields of underwater protection of various engineering equipment and facilities, underwater emergency repair and the like.
Description
Technical Field
The invention belongs to the technical field of underwater protective coatings, and particularly relates to an underwater construction curing coating, and a preparation method and application thereof.
Background
Engineering equipment and facilities in an underwater soaking environment are influenced by severe environments such as soaking corrosion of water, microbial corrosion and the like for a long time, so that the design service life of the engineering equipment and facilities cannot be reached, and potential safety hazards exist. Since a large number of underwater engineering structures are immovable, how to improve the durability of such engineering equipment and facilities is an important issue.
The underwater paint is a paint which can be coated and cured underwater, and the matrix resin of the paint mainly comprises polyester resin, vinyl resin and epoxy resin. However, coatings formed from polyester resin systems are susceptible to damage upon impact. The vinyl resin system requires the addition of a solvent, and is incompletely cured in water and causes environmental pollution. Therefore, most of the existing underwater coatings use epoxy resin as matrix resin. At present, researchers have developed some underwater epoxy coatings capable of coating and curing under water, but these underwater epoxy coatings have the following problems: after underwater coating, the coating needs longer curing time and is not cured completely, water between the coating and the surface of the base material cannot be drained completely, the environmental suitability is poor, and the formed coating has poor toughness, is easy to foam, has poor adhesion to the surface of the base material and the like. Therefore, the developed underwater construction curing coating with fast curing, high adhesive force and excellent environmental adaptability has important significance for underwater protection of various engineering equipment and facilities, underwater emergency repair and the like.
Disclosure of Invention
The invention aims to overcome the defects of slow and incomplete underwater curing, poor coating adhesion and the like of the conventional anticorrosive coating and provide the underwater construction curing coating. The underwater construction curing coating has the characteristics of quick curing, high adhesive force and heavy corrosion resistance.
The invention also aims to provide a preparation method of the curing coating for underwater construction.
Still another object of the present invention is to provide the use of the above-mentioned curing coating for underwater construction.
The purpose of the invention is realized by the following technical scheme:
an underwater construction curing coating comprises a component A and a component B;
wherein the component A comprises the following components in parts by weight:
the epoxy resin comprises at least one of bisphenol A type epoxy resin E-03, bisphenol A type epoxy resin E-12, bisphenol A type epoxy resin E-20, bisphenol A type epoxy resin E-51, bisphenol A type epoxy resin E-44, novolac epoxy resin F-51, novolac epoxy resin F-44, novolac epoxy resin F-48, epoxy oligosiloxane and hyperbranched epoxy resin; more preferably at least one of bisphenol A epoxy resin E-51, bisphenol A epoxy resin E-44, novolac epoxy resin F-51, novolac epoxy resin F-44, novolac epoxy resin F-48, epoxy oligosiloxane and hyperbranched epoxy resin.
The epoxy oligosiloxane is preferably prepared by reacting an organosilane compound, absolute ethyl alcohol, concentrated hydrochloric acid and water at 60-80 ℃ for 6-12 hours under the condition of stirring, and removing redundant hydrochloric acid, absolute ethyl alcohol and water through reduced pressure distillation at 60-80 ℃.
The organosilane is preferably at least one of tetraethyl silicate, tetramethyl silicate, dimethyldimethoxysilane, dodecyltriethoxysilane, tetrabutyl silicate, methyltrimethoxysilane, benzyltriethoxysilane, ethyltriethoxysilane, isobutyltriethoxysilane, hexyltrimethoxysilane, hexadecyltrimethoxysilane, dimethoxy (meth) phenylsilane, allyltrimethoxysilane, methylvinyldiethoxysilane, phenyltriethoxysilane, diethoxydiphenylsilane, diphenyldimethoxysilane, vinyltrimethoxysilane, gamma-glycidoxypropyltrimethoxysilane and 2- (3, 4-epoxycyclohexyl) ethyltrimethoxysilane. Wherein gamma-glycidoxypropyltrimethoxysilane and 2- (3, 4-epoxycyclohexyl) ethyltrimethoxysilane account for 20-100% of the total mass of the organosilane
The weight ratio of the organosilane to the absolute ethyl alcohol to the concentrated hydrochloric acid to the water is preferably 70-77: 18-22: 1-1.5: 4-6; more preferably in a weight ratio of 73.5:20:1.5: 5.
The hyperbranched epoxy resin is prepared by heating, stirring and reacting a glycidyl ether compound, 1,1, 1-tri (hydroxymethyl) ethane and tetra-n-butylammonium chloride at 120 ℃ for 12 hours.
The glycidyl ether compound preferably includes at least one of 1, 6-hexanediol diglycidyl ether, neopentyl glycol diglycidyl ether, resorcinol diglycidyl ether, ethylene glycol diglycidyl ether, and 1, 4-butanediol diglycidyl ether.
The weight ratio of the glycidyl ether compound to the 1,1, 1-tri (hydroxymethyl) ethane to the tetra-n-butylammonium chloride is preferably 68-78: 16-24: 6-8.
The reactive solvent preferably comprises at least one of C12-14 glycidyl ether, benzyl glycidyl ether, 1, 4-cyclohexanedimethanol diglycidyl ether, trimethylolpropane triglycidyl ether, neopentyl glycol diglycidyl ether, and o-tolyl glycidyl ether; more preferably, the glycidyl ether compound includes at least one of benzyl glycidyl ether, 1, 4-cyclohexanedimethanol diglycidyl ether, o-tolyl glycidyl ether, C12-14 glycidyl ether, and neopentyl glycol diglycidyl ether.
The hydrophobic modifier preferably comprises: at least one of simethicone, fluorosilicone oil, liquid fluororesin, petroleum resin, liquefied paraffin and oleic acid;
the pigment and filler is preferably at least one of magnesium carbonate, talcum powder, mica powder, precipitated barium sulfate, wollastonite, silicon carbide, silica micropowder, light calcium carbonate, titanium dioxide, iron oxide red, aluminum oxide, zinc oxide and calcium oxide.
The auxiliary agent comprises a wetting dispersant, a leveling agent and a thixotropic agent.
The wetting and dispersing agent preferably comprises at least one of BYK-P2710 and BYK-P104S, MOK-5012.
The leveling agent is preferably at least one of BYK-361N, BYK-342 and D.E. 837.
The thixotropic agent preferably comprises at least one of polyamide wax, fumed silica and organobentonite.
The component B comprises the following components in parts by weight:
40-80 parts of hyperbranched polythiol;
16-57 parts of an amine curing agent;
2-10 parts of an accelerator.
The hyperbranched polythiol is preferably prepared by reacting organosilane, absolute ethyl alcohol, concentrated hydrochloric acid and water at 60-80 ℃ for 4-12 h under the stirring condition, and removing redundant hydrochloric acid, absolute ethyl alcohol and water through reduced pressure distillation at 60-80 ℃.
The organosilane preferably comprises at least one of gamma-mercaptopropyltriethoxysilane, gamma-mercaptopropyltrimethoxysilane, gamma-mercaptopropylmethyldimethoxysilane, tetraethyl silicate, tetramethyl silicate, dimethyldimethoxysilane, dodecyltriethoxysilane, tetrabutyl silicate, methyltrimethoxysilane, benzyltriethoxysilane, ethyltriethoxysilane, isobutyltriethoxysilane, hexyltrimethoxysilane, hexadecyltrimethoxysilane, dimethoxy (methyl) phenylsilane, allyltrimethoxysilane, methylvinyldiethoxysilane, phenyltriethoxysilane, diethoxydiphenylsilane, diphenyldimethoxysilane, vinyltrimethoxysilane. Wherein the gamma-mercaptopropyltriethoxysilane, the gamma-mercaptopropyltrimethoxysilane and the gamma-mercaptopropylmethyldimethoxysilane account for 40-100% of the total mass of the organosilane.
The organosilane, the absolute ethyl alcohol, the concentrated hydrochloric acid and the water are preferably calculated according to the weight ratio of 63.5-84: 10-30: 1-1.5: 5.
The component B can also comprise a polythiol curing agent; the polythiol curing agent can be at least one of polythiol QE-340M, polythiol Capcure 3800 and polythiol GPM-800.
The amine curing agent is preferably at least one of m-xylylenediamine, 4 '-diaminodiphenylmethane, 4' -diaminodicyclohexylmethane, oleylamine, polyamide 650, polyamide 651, phenolaldehyde amine 810, phenolaldehyde amine 910, phenolaldehyde amine T31, phenolaldehyde amine T33 and phenolaldehyde amine T316.
The accelerator is preferably at least one of 2,4, 6-tris (dimethylaminomethyl) phenol, 1-methylimidazole, triethanolamine, N-dimethylbenzylamine, triethylamine, 4-methylimidazole and 2-methyl-4-ethylimidazole.
The preparation method of the underwater construction curing coating comprises the following steps:
(1) preparing epoxy oligosiloxane, hyperbranched epoxy resin and hyperbranched polythiol;
(2) uniformly mixing 30-50 parts of epoxy resin, 5-10 parts of reactive solvent, 3-10 parts of hydrophobic modifier, 30-60 parts of pigment and filler and 2-7 parts of auxiliary agent to obtain a component A;
(3) uniformly mixing 40-80 parts of hyperbranched polythiol, 20-50 parts of amine curing agent and 2-10 parts of accelerator to obtain a component B;
(4) and uniformly mixing the component A and the component B according to the mass ratio of 100: 20-40 to obtain the underwater construction curing coating.
The underwater construction curing coating is applied to underwater protection and/or emergency repair.
The underwater protection and/or emergency repair refers to the underwater protection and/or emergency repair of various engineering equipment and facilities.
The novel concept of function densification of the underwater construction curing coating is shown as a formula I, and by taking the synthesis of hyperbranched polythiol by using gamma-mercaptopropyl trimethoxy silane as an example, the content of sulfydryl in a unit mass material is obviously higher; in addition, the mercapto group and the epoxy group can react quickly under the action of a tertiary amine catalyst, and the mechanism is shown as a formula II.
Formula I: hyperbranched polythiol synthesis reaction formula
Formula II: rapid reaction mechanism of mercapto group and epoxy group
Compared with the prior art, the invention has the following outstanding advantages and effects:
(1) the underwater construction curing coating is prepared based on a new idea of function densification and a rapid reaction mechanism of sulfydryl and an epoxy group, and the polythiol curing agent with a hyperbranched structure is prepared. Different from the curing reaction of the traditional amine curing agent and epoxy resin, the hyperbranched polythiol has higher reaction rate with the epoxy group under the action of the curing accelerator, and the curing reaction is not influenced by water, so that the blocking effect of water on the curing of the curing material for underwater construction in the environment can be greatly reduced.
(2) The invention adopts the mercapto oligosiloxane with a hyperbranched structure as the polythiol curing agent, the special molecular structure ensures that the curing agent has higher functional group density, and the curing agent can quickly react with epoxy resin under the condition of matching with an accelerant, thereby greatly reducing the blocking effect of environmental water on material curing, and further realizing the quick curing function of the underwater construction curing coating.
(3) The underwater construction curing coating adopts the unique hydrophobic modifier to ensure that a material system has high hydrophobicity, can weaken the negative influence of water on material curing, can effectively remove a water film on the surface of the substrate through an interface effect, enables the coating and the substrate to be tightly attached, and realizes strong adhesion between the coating and the substrate by cooperating with a highly crosslinked coating structure formed by the densification of the functions of the hyperbranched polythiol curing agent.
(4) According to the invention, the epoxy resin and the hyperbranched polythiol are used as a matrix resin system, besides hydroxyl ether bonds and the like on the main chain of the epoxy resin, a large number of silicon hydroxyl groups are contained on the side chain of the hyperbranched polythiol, and the side chain of the hyperbranched polythiol can be dehydrated and condensed with the hydroxyl groups on the substrate to form chemical bonds, so that the adhesive force of the coating is greatly improved. And silicon hydroxyl on the side chain of the hyperbranched polythiol can also be dehydrated and condensed with hydroxyl on the pigment and filler to form a chemical bond, so that the interaction force between the filler and the resin is increased, and the coating has high hardness, good wear resistance, strong barrier capability to corrosive ions and strong corrosion resistance.
(5) The curing coating for underwater construction can obtain hyperbranched polythiol curing agents with different structures by controlling the reaction of mercaptosilane and silane compounds with different side groups, thereby improving the toughness and impact resistance of the coating.
Detailed Description
The present invention will be described in further detail with reference to examples, but the embodiments of the present invention are not limited thereto. The raw material parts in the following examples are parts by weight.
Example 1
A preparation method of an underwater construction curing coating comprises the following steps:
(1) adding 54 parts by weight of tetramethyl silicate, 30 parts by weight of gamma-mercaptopropyl trimethoxysilane, 10 parts by weight of absolute ethyl alcohol, 5 parts by weight of deionized water and 1 part by weight of concentrated hydrochloric acid into a reaction kettle, heating and stirring at 60 ℃ for reaction for 6 hours, and removing hydrochloric acid, ethanol and water in a system by reduced pressure distillation at 60 ℃ to obtain hyperbranched polythiol;
(2) uniformly mixing 38 parts by weight of bisphenol A type epoxy resin E-51, 5 parts by weight of benzyl glycidyl ether, 5 parts by weight of liquefied paraffin, 30 parts by weight of light magnesium carbonate, 15 parts by weight of talcum powder, 5 parts by weight of titanium dioxide, 1 part by weight of polyamide wax, 0.45 part by weight of BYK-361N and 0.55 part by weight of BYK-P104S to obtain a component A;
(3) uniformly mixing 43 parts by weight of hyperbranched polythiol, 55 parts by weight of phenolic aldehyde amine T31 and 2 parts by weight of 2,4, 6-tris (dimethylaminomethyl) phenol to obtain a component B;
(4) when in use, the component A and the component B are stirred and mixed uniformly according to the weight ratio of 100:20 to obtain the underwater construction curing coating.
Example 2
A preparation method of an underwater construction curing coating comprises the following steps:
(1) adding 23.5 parts by weight of methyltrimethoxysilane, 20 parts by weight of diphenyldimethoxysilane, 20 parts by weight of gamma-mercaptopropyltriethoxysilane, 30 parts by weight of absolute ethyl alcohol, 5 parts by weight of deionized water and 1.5 parts by weight of concentrated hydrochloric acid into a reaction kettle, heating and stirring for reaction at 60 ℃ for 6 hours, and distilling under reduced pressure at 60 ℃ to remove hydrochloric acid, ethanol and water in a system to obtain hyperbranched polythiol;
(2) uniformly mixing 40 parts by weight of novolac epoxy resin F-51, 8 parts by weight of C12-14 glycidyl ether, 3 parts by weight of dimethyl silicone oil, 30 parts by weight of alumina, 11.5 parts by weight of mica powder, 5 parts by weight of iron oxide red, 1.5 parts by weight of organic bentonite, 0.45 part by weight of BYK-342 and 0.55 part by weight of BYK-P104S to obtain a component A;
(3) uniformly mixing 38 parts by weight of hyperbranched polythiol, 10 parts by weight of polythiol QE-340M (available from Toray corporation), 39 parts by weight of 4,4' -diaminodiphenylmethane, 10 parts by weight of M-xylylenediamine, and 3 parts by weight of triethylamine to obtain a component B;
(4) when in use, the component A and the component B are stirred and mixed uniformly according to the weight ratio of 100:23 to obtain the curing coating for underwater construction.
Example 3
A preparation method of an underwater construction curing coating comprises the following steps:
(1) adding 78 parts by weight of resorcinol diglycidyl ether, 16 parts by weight of 1,1, 1-tri (hydroxymethyl) ethane and 6 parts by weight of tetra-n-butylammonium chloride into a reaction kettle, heating and stirring at 120 ℃, reacting for 12 hours, and performing extraction separation, drying and water removal to obtain hyperbranched epoxy resin;
(2) adding 13.5 parts by weight of methyltrimethoxysilane, 20 parts by weight of diphenyldimethoxysilane, 40 parts by weight of gamma-mercaptopropylmethyldimethoxysilane, 20 parts by weight of absolute ethyl alcohol, 5 parts by weight of deionized water and 1.5 parts by weight of concentrated hydrochloric acid into a reaction kettle, heating and stirring at 60 ℃ for reaction for 6 hours, and removing hydrochloric acid, ethanol and water in a system through reduced pressure distillation at 70 ℃ to obtain hyperbranched polythiol;
(3) uniformly mixing 35 parts by weight of bisphenol A type epoxy resin E-44, 10 parts by weight of hyperbranched epoxy resin, 5 parts by weight of C12-14 glycidyl ether, 4 parts by weight of fluorosilicone oil, 26.3 parts by weight of silica powder, 10 parts by weight of mica powder, 5.7 parts by weight of titanium dioxide, 3 parts by weight of fumed silica, 0.45 part by weight of BYK-361N and 0.55 part by weight of BYK-P2710 to obtain a component A;
(4) uniformly mixing 45 parts by weight of hyperbranched polythiol, 37.5 parts by weight of polyamide 651, 15 parts by weight of 4,4' -diaminodicyclohexylmethane and 2.5 parts by weight of 2-methyl-4-ethylimidazole to obtain a component B;
(5) when in use, the component A and the component B are stirred and mixed uniformly according to the weight ratio of 100:35 to obtain the underwater construction curing coating.
Example 4
A preparation method of an underwater construction curing coating comprises the following steps:
(1) adding 20 parts by weight of phenyltriethoxysilane, 60 parts by weight of gamma-mercaptopropyltriethoxysilane, 13.5 parts by weight of absolute ethyl alcohol, 5 parts by weight of deionized water and 1.5 parts by weight of concentrated hydrochloric acid into a reaction kettle, heating and stirring at 80 ℃ for reaction for 4 hours, and distilling under reduced pressure at 60 ℃ to remove hydrochloric acid, ethanol and water in a system to obtain hyperbranched polythiol;
(2) uniformly mixing 50 parts by weight of novolac epoxy resin F-44, 5 parts by weight of o-tolyl glycidyl ether, 3 parts by weight of petroleum resin, 25 parts by weight of silicon carbide, 10 parts by weight of wollastonite, 5 parts by weight of iron oxide red, 1 part by weight of fumed silica, 0.45 part by weight of moderate 837 and 0.55 part by weight of MOK-5012 to obtain a component A;
(3) uniformly mixing 50 parts by weight of hyperbranched polythiol, 5 parts by weight of polythiol Capture 3800 (purchased from Corning chemical (China) Co., Ltd.), 41 parts by weight of phenalkamine 810 and 4 parts by weight of 2,4, 6-tris (dimethylaminomethyl) phenol to obtain a component B;
(4) when in use, the component A and the component B are stirred and mixed uniformly according to the weight ratio of 100:26 to obtain the curing coating for underwater construction.
Example 5
A preparation method of an underwater construction curing coating comprises the following steps:
(1) adding 68 parts by weight of ethylene glycol diglycidyl ether, 24 parts by weight of 1,1, 1-tri (hydroxymethyl) ethane and 8 parts by weight of tetra-n-butylammonium chloride into a reaction kettle, heating and stirring at 120 ℃, reacting for 12 hours, and performing extraction separation, drying and water removal to obtain hyperbranched epoxy resin;
(2) adding 20 parts by weight of methyltrimethoxysilane, 60 parts of gamma-mercaptopropyltrimethoxysilane, 13.5 parts of absolute ethyl alcohol, 5 parts of deionized water and 1.5 parts of concentrated hydrochloric acid into a reaction kettle, heating and stirring at 60 ℃, reacting for 12 hours, and distilling at 70 ℃ under reduced pressure to remove hydrochloric acid, ethanol and water in a system to obtain hyperbranched polythiol;
(3) uniformly mixing 35 parts by weight of novolac epoxy resin F-48, 6 parts by weight of hyperbranched epoxy resin, 10 parts by weight of 1, 4-cyclohexanedimethanol diglycidyl ether, 3 parts by weight of oleic acid, 27 parts by weight of light magnesium carbonate, 8 parts by weight of zinc oxide, 5 parts by weight of titanium dioxide, 5 parts by weight of polyamide wax, 0.45 part by weight of a pretty 837 and 0.55 part by weight of BYK-P2710 to obtain a component A;
(4) uniformly mixing 70 parts by weight of hyperbranched polythiol, 27 parts by weight of polyamide 650 and 3 parts by weight of triethanolamine to obtain a component B;
(5) when in use, the component A and the component B are stirred and mixed uniformly according to the weight ratio of 100:40 to obtain the underwater construction curing coating.
Example 6
A preparation method of an underwater construction curing coating comprises the following steps:
(1) adding 13.5 parts by weight of methyltrimethoxysilane, 20 parts by weight of diphenyldimethoxysilane, 40 parts by weight of gamma-glycidoxypropyltrimethoxysilane, 20 parts by weight of absolute ethyl alcohol, 5 parts by weight of deionized water and 1.5 parts by weight of concentrated hydrochloric acid into a reaction kettle, heating and stirring at 80 ℃ for reacting for 8 hours, and distilling at 70 ℃ under reduced pressure to remove hydrochloric acid, ethanol and water in the system to obtain the epoxy oligosiloxane;
(2) adding 20 parts by weight of dimethyl dimethoxysilane, 10 parts by weight of tetramethyl silicate, 50 parts by weight of gamma-mercaptopropyl-methyl-dimethoxysilane, 13.5 parts by weight of absolute ethyl alcohol, 5 parts by weight of deionized water and 1.5 parts by weight of concentrated hydrochloric acid into a reaction kettle, heating and stirring the mixture to react for 12 hours at the temperature of 60 ℃, and distilling the mixture under reduced pressure at the temperature of 60 ℃ to remove hydrochloric acid, ethanol and water in a system to obtain hyperbranched polythiol;
(3) uniformly mixing 30 parts by weight of bisphenol A type epoxy resin E-51, 8 parts by weight of epoxy oligosiloxane, 5 parts by weight of o-tolyl glycidyl ether, 4 parts by weight of liquid fluororesin, 30 parts by weight of light calcium carbonate, 15 parts by weight of precipitated barium sulfate, 5 parts by weight of titanium dioxide, 2 parts by weight of fumed silica, 0.45 part by weight of a moderate 837 and 0.55 part by weight of BYK-P104S solution to obtain a component A;
(4) uniformly mixing 60 parts by weight of hyperbranched polythiol, 20 parts by weight of 4,4' -diaminodicyclohexylmethane, 15 parts by weight of phenolic aldehyde amine 910 and 5 parts by weight of 1-methylimidazole to obtain a component B;
(5) when in use, the component A and the component B are stirred and mixed uniformly according to the weight ratio of 100:33 to obtain the underwater construction curing coating.
Example 7
A preparation method of an underwater construction curing coating comprises the following steps:
(1) adding 20 parts by weight of hexadecyl trimethoxy silane, 60 parts by weight of gamma-mercaptopropyl triethoxysilane, 13.5 parts by weight of absolute ethyl alcohol, 5 parts by weight of deionized water and 1.5 parts by weight of concentrated hydrochloric acid into a reaction kettle, heating and stirring at 60 ℃, reacting for 12 hours, and distilling at 60 ℃ under reduced pressure to remove hydrochloric acid, ethanol and water in a system to obtain hyperbranched polythiol;
(2) uniformly mixing 30 parts by weight of novolac epoxy resin F-51, 5 parts by weight of C12-14 glycidyl ether, 3 parts by weight of fluorosilicone oil, 40 parts by weight of zinc oxide, 15 parts by weight of silicon micropowder, 5 parts by weight of iron oxide red, 1 part by weight of organic bentonite, 0.45 part by weight of BYK-361N and 0.55 part by weight of MOK-5012 to obtain a component A;
(3) uniformly mixing 40 parts by weight of hyperbranched polythiol, 35 parts by weight of phenolic amine 910, 22 parts by weight of oleylamine and 3 parts by weight of N, N-dimethylbenzylamine to obtain a component B;
(4) when in use, the component A and the component B are stirred and mixed uniformly according to the weight ratio of 100:25 to obtain the curing coating for underwater construction.
Example 8
A preparation method of an underwater construction curing coating comprises the following steps:
(1) adding 79 parts by weight of gamma-mercaptopropyl-trimethoxysilane, 15 parts by weight of absolute ethyl alcohol, 5 parts by weight of deionized water and 1 part by weight of concentrated hydrochloric acid into a reaction kettle, heating and stirring for reaction for 10 hours at 60 ℃, and carrying out reduced pressure distillation at 60 ℃ to remove hydrochloric acid, ethyl alcohol and water in a system to obtain hyperbranched polythiol;
(2) uniformly mixing 35 parts by weight of bisphenol A type epoxy resin E-44, 5 parts by weight of neopentyl glycol diglycidyl ether, 10 parts by weight of petroleum resin, 37 parts by weight of talcum powder, 5 parts by weight of calcium oxide, 5 parts by weight of titanium dioxide, 2 parts by weight of polyamide wax, 0.45 part by weight of BYK-342 and 0.55 part by weight of BYK-P2710 to obtain a component A;
(3) uniformly mixing 60 parts by weight of hyperbranched polythiol, 20 parts by weight of polythiol GPM-800 (purchased from Gabriel Performance Products company), 16 parts by weight of m-xylylenediamine and 4 parts by weight of 2,4, 6-tris (dimethylaminomethyl) phenol to obtain a component B;
(4) when in use, the component A and the component B are stirred and mixed uniformly according to the weight ratio of 100:30 to obtain the underwater construction curing coating.
Performance test
The cured coatings obtained in examples 1 to 8 were respectively cured by underwater brush coating and subjected to performance tests, and the results are shown in table 1, in which:
the surface dry time and the actual dry time are determined according to the dry time measurement method of GB/T1728-1979 paint films and putty films.
Water contact angle: testing the static water contact angle of the paint film by using a Theta Auto 113 type contact angle tester;
adhesion force: testing the adhesion force according to GB/T5210-2006 paint and varnish pull-off method;
flexibility: paint flexibility assay was tested according to GB/T1731-1993.
Water resistance: the paint film water resistance assay was tested according to GB/T1733-one 1993.
Table 1:
as can be seen from Table 1, the underwater construction curing coating has the characteristic of fast curing due to the addition of the hyperbranched polythiol with very high mercapto density, and the surface drying time and the actual drying time of the coating can reach 0.8h and 2h at the shortest. By adding the unique hydrophobic modifier, the material has stronger hydrophobicity, and the water contact angles are all above 85 degrees. Meanwhile, the chemical structure of the hyperbranched polythiol can be designed, so that the underwater construction curing coating has good flexibility. Because the curing coating for underwater construction has high crosslinking density, the adhesive force of the coating under water can reach 4.3MPa at least and 6.8MPa at most, and the coating has excellent water resistance. The underwater construction curing coating has the characteristics of underwater rapid curing and hydrophobicity, and a high-performance protective coating can be obtained after the underwater construction curing.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such modifications are intended to be included in the scope of the present invention.
Claims (10)
1. The underwater construction curing coating is characterized by comprising a component A and a component B;
wherein the component A comprises the following components in parts by weight:
the component B comprises the following components in parts by weight:
40-80 parts of hyperbranched polythiol;
16-57 parts of an amine curing agent;
2-10 parts of an accelerator.
2. The underwater construction cured coating of claim 1, wherein the epoxy resin comprises at least one of bisphenol a epoxy resin E-03, bisphenol a epoxy resin E-12, bisphenol a epoxy resin E-20, bisphenol a epoxy resin E-51, bisphenol a epoxy resin E-44, novolac epoxy resin F-51, novolac epoxy resin F-44, novolac epoxy resin F-48, epoxy oligosiloxane, and hyperbranched epoxy resin.
3. The underwater construction curing coating of claim 2,
the epoxy oligosiloxane is prepared by reacting an organosilane compound, absolute ethyl alcohol, concentrated hydrochloric acid and water at 60-80 ℃ for 6-12 hours under the condition of stirring, and removing redundant hydrochloric acid, absolute ethyl alcohol and water through reduced pressure distillation at 60-80 ℃ to obtain the epoxy oligosiloxane;
the organosilane is at least one of tetraethyl silicate, tetramethyl silicate, dimethyl dimethoxy silane, dodecyl triethoxy silane, tetrabutyl silicate, methyl trimethoxy silane, benzyl triethoxy silane, ethyl triethoxy silane, isobutyl triethoxy silane, hexyl trimethoxy silane, hexadecyl trimethoxy silane, dimethoxy (methyl) phenyl silane, allyl trimethoxy silane, methyl vinyl diethoxy silane, phenyl triethoxy silane, diethoxy diphenyl silane, diphenyl dimethoxy silane, vinyl trimethoxy silane, gamma-glycidyl ether oxypropyl trimethoxy silane and 2- (3, 4-epoxy cyclohexyl) ethyl trimethoxy silane; wherein gamma-glycidoxypropyltrimethoxysilane and 2- (3, 4-epoxycyclohexyl) ethyltrimethoxysilane account for 20-100% of the total mass of the organosilane;
the weight ratio of the organosilane to the absolute ethyl alcohol to the concentrated hydrochloric acid to the water is 70-77: 18-22: 1-1.5: 4-6.
4. The underwater construction curing coating of claim 2,
the hyperbranched epoxy resin is obtained by heating, stirring and reacting a glycidyl ether compound, 1,1, 1-tri (hydroxymethyl) ethane and tetra-n-butylammonium chloride for 12 hours at 120 ℃;
the glycidyl ether compound comprises at least one of 1, 6-hexanediol diglycidyl ether, neopentyl glycol diglycidyl ether, resorcinol diglycidyl ether, ethylene glycol diglycidyl ether and 1, 4-butanediol diglycidyl ether;
the weight ratio of the glycidyl ether compound to the 1,1, 1-tri (hydroxymethyl) ethane to the tetra-n-butylammonium chloride is 68-78: 16-24: 6-8.
5. The underwater construction curing coating of claim 1,
the reactive solvent comprises at least one of C12-14 glycidyl ether, benzyl glycidyl ether, 1, 4-cyclohexanedimethanol diglycidyl ether, trimethylolpropane triglycidyl ether, neopentyl glycol diglycidyl ether and o-tolyl glycidyl ether;
the hydrophobic modifier comprises: at least one of simethicone, fluorosilicone oil, liquid fluororesin, petroleum resin, liquefied paraffin and oleic acid;
the pigment and filler is at least one of magnesium carbonate, talcum powder, mica powder, precipitated barium sulfate, wollastonite, silicon carbide, silica micropowder, light calcium carbonate, titanium dioxide, iron oxide red, aluminum oxide, zinc oxide and calcium oxide;
the auxiliary agent comprises a wetting dispersant, a flatting agent and a thixotropic agent;
the wetting dispersant comprises at least one of BYK-P2710 and BYK-P104S, MOK-5012;
the leveling agent is at least one of BYK-361N, BYK-342 and a humate 837;
the thixotropic agent comprises at least one of polyamide wax, fumed silica and organic bentonite.
6. The underwater construction curing coating of claim 1,
the hyperbranched polythiol is prepared by reacting organosilane, absolute ethyl alcohol, concentrated hydrochloric acid and water at the temperature of 60-80 ℃ for 4-12 hours under the stirring condition, and carrying out reduced pressure distillation at the temperature of 60-80 ℃ to remove redundant hydrochloric acid, absolute ethyl alcohol and water;
the organosilane comprises at least one of gamma-mercaptopropyltriethoxysilane, gamma-mercaptopropyltrimethoxysilane, gamma-mercaptopropylmethyldimethoxysilane, tetraethyl silicate, tetramethyl silicate, dimethyldimethoxysilane, dodecyltriethoxysilane, tetrabutyl silicate, methyltrimethoxysilane, benzyltriethoxysilane, ethyltriethoxysilane, isobutyltriethoxysilane, hexyltrimethoxysilane, hexadecyltrimethoxysilane, dimethoxy (methyl) phenylsilane, allyltrimethoxysilane, methylvinyldiethoxysilane, phenyltriethoxysilane, diethoxydiphenylsilane, diphenyldimethoxysilane, vinyltrimethoxysilane; wherein the gamma-mercaptopropyltriethoxysilane, the gamma-mercaptopropyltrimethoxysilane and the gamma-mercaptopropylmethyldimethoxysilane account for 40-100% of the total mass of the organosilane;
the weight ratio of the organosilane to the absolute ethyl alcohol to the concentrated hydrochloric acid to the water is 63.5-84: 10-30: 1-1.5: 5.
7. The underwater construction curing coating of claim 6,
the component B also comprises a polythiol curing agent; the polythiol curing agent is at least one of polythiol QE-340M, polythiol Capcure 3800 and polythiol GPM-800.
8. The underwater construction curing coating of claim 6,
the amine curing agent is at least one of m-xylylenediamine, 4 '-diaminodiphenylmethane, 4' -diaminodicyclohexylmethane, oleylamine, polyamide 650, polyamide 651, phenolic amine 810, phenolic amine 910, phenolic amine T31, phenolic amine T33 and phenolic amine T316;
the accelerant is at least one of 2,4, 6-tri (dimethylaminomethyl) phenol, 1-methylimidazole, triethanolamine, N-dimethylbenzylamine, triethylamine, 4-methylimidazole and 2-methyl-4-ethylimidazole.
9. The preparation method of the underwater construction curing coating as claimed in any one of claims 1 to 8, characterized by comprising the following steps:
(1) preparing epoxy oligosiloxane, hyperbranched epoxy resin and hyperbranched polythiol;
(2) uniformly mixing 30-50 parts of epoxy resin, 5-10 parts of reactive solvent, 3-10 parts of hydrophobic modifier, 30-60 parts of pigment and filler and 2-7 parts of auxiliary agent to obtain a component A;
(3) uniformly mixing 40-80 parts of hyperbranched polythiol, 20-50 parts of amine curing agent and 2-10 parts of accelerator to obtain a component B;
(4) and uniformly mixing the component A and the component B according to the mass ratio of 100: 20-40 to obtain the underwater construction curing coating.
10. Use of the cured coating for underwater construction according to any one of claims 1 to 9 in underwater protection and/or emergency repair.
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