CN112708323A - Hyperbranched modified epoxy resin finish paint with high weather resistance and preparation method thereof - Google Patents
Hyperbranched modified epoxy resin finish paint with high weather resistance and preparation method thereof Download PDFInfo
- Publication number
- CN112708323A CN112708323A CN202011571504.0A CN202011571504A CN112708323A CN 112708323 A CN112708323 A CN 112708323A CN 202011571504 A CN202011571504 A CN 202011571504A CN 112708323 A CN112708323 A CN 112708323A
- Authority
- CN
- China
- Prior art keywords
- epoxy resin
- stirring
- hyperbranched
- parts
- minutes
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- 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
- C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
-
- 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
- C08G59/02—Polycondensates containing more than one epoxy group per molecule
- C08G59/04—Polycondensates containing more than one epoxy group per molecule of polyhydroxy compounds with epihalohydrins or precursors thereof
-
- 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
- C08G59/02—Polycondensates containing more than one epoxy group per molecule
- C08G59/04—Polycondensates containing more than one epoxy group per molecule of polyhydroxy compounds with epihalohydrins or precursors thereof
- C08G59/06—Polycondensates containing more than one epoxy group per molecule of polyhydroxy compounds with epihalohydrins or precursors thereof of polyhydric phenols
- C08G59/063—Polycondensates containing more than one epoxy group per molecule of polyhydroxy compounds with epihalohydrins or precursors thereof of polyhydric phenols with epihalohydrins
-
- 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
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/61—Additives non-macromolecular inorganic
-
- 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
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/61—Additives non-macromolecular inorganic
- C09D7/62—Additives non-macromolecular inorganic modified by treatment with other compounds
-
- 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
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/70—Additives characterised by shape, e.g. fibres, flakes or microspheres
Abstract
The invention discloses a hyperbranched modified epoxy resin finish paint with strong weather resistance and a preparation method thereof, wherein the hyperbranched modified epoxy resin finish paint comprises the following raw materials in parts by weight: 55-65 parts of hyperbranched epoxy resin, 20-30 parts of diluent, 20-30 parts of filler, 5-8 parts of dispersing agent, 15-25 parts of curing agent and 0.5-1 part of flatting agent; the hyperbranched epoxy resin can be matched with conventional components in the market for use, so that the cost of additionally researching and developing matched fillers is reduced, and the synergistic effect among the materials is obvious; the hyperbranched modified epoxy resin finish paint with strong weather resistance provided by the invention takes hyperbranched epoxy resin as a base material and can improve the crosslinking density of a coating, increase the hardness and adhesive force of a paint film and improve the flexibility and aging resistance of the paint film.
Description
Technical Field
The invention relates to the technical field of high polymers and coatings, in particular to hyperbranched modified epoxy resin finish with strong weather resistance and a preparation method thereof.
Background
The hyperbranched polymer has a structure similar to that of a dendritic polymer, is a regular highly branched macromolecule with a three-dimensional branched structure, and has a compact structure similar to a sphere in molecules, small hydrodynamic gyration radius, high branching degree and less molecular chain entanglement, so that the viscosity change is not large, the change cannot be rapidly changed along with the increase of relative molecular mass, and theoretically, the application of the hyperbranched polymer in a coating is possible; however, since the molecular weight of the hyperbranched polymer is large, the viscosity of the hyperbranched polymer does not change much with the increase of the molecular weight, but the basic viscosity is large, and the application range of the hyperbranched polymer is limited.
The epoxy resin is a high molecular compound containing an epoxy group in a molecular structure, the cured epoxy resin has good physical and chemical properties and excellent bonding viscosity on the surfaces of metal and non-metal materials, so the epoxy resin is widely applied to various departments of national defense and national economy, the hyperbranched epoxy resin is slow to develop, firstly, the functionality of the epoxy resin in the current market is generally between 2 and 4, a paint film with high crosslinking density cannot be effectively formed, or the viscosity of the formed paint film is high, so that the application of the epoxy resin in the field of paint is influenced; secondly, the existing hyperbranched epoxy resin compound has unreasonable structural design, high hydroxyl functionality and strong polarity, strong hydrogen bonds are easily formed between molecules, the compound is easy to agglomerate and can not be effectively dispersed in the coating, and in addition, the problem of poor direct compatibility between the hyperbranched epoxy resin and auxiliary materials can also occur; finally, the development of the special epoxy resin is slow, and certain special fields in the market provide higher requirements for the acid and alkali resistance, hardness, friction resistance, chemical corrosion resistance and aging resistance of the special epoxy resin.
Disclosure of Invention
In order to solve the problems, the invention aims to provide a hyperbranched modified epoxy resin finish with strong weather resistance and a preparation method thereof.
In order to achieve the purpose, the invention is realized by the following technical scheme:
a hyperbranched modified epoxy resin finish paint with strong weather resistance is composed of the following raw materials in parts by weight: 55-65 parts of hyperbranched epoxy resin, 20-30 parts of diluent, 20-30 parts of filler, 5-8 parts of dispersing agent, 15-25 parts of curing agent and 0.5-1 part of flatting agent;
the hyperbranched epoxy resin is prepared by the following steps:
dissolving triethanolamine in N, N-dimethylformamide, stirring, cooling to 0-5 ℃, adding sodium hydride, stirring for 10 minutes, adding epoxy chloropropane at the temperature, stirring for at least 30 minutes, heating to 20-25 ℃, stirring for reaction for 2-3 hours, adding distilled water, stirring for 30-40 minutes, adding ethyl acetate, stirring for 20-30 minutes, standing for layering, adding water into an organic phase, extracting and washing, standing for layering, removing a solvent by virtue of vacuum distillation of the organic phase, and recrystallizing the obtained solid with methanol to obtain tris (2- (epoxy-2-methoxy) ethoxy) amine;
wherein the mass volume ratio of the trihydroxyethylamine to the N, N-dimethylformamide to the sodium hydride to the epichlorohydrin to the distilled water to the ethyl acetate is 140-150 g: 1.5-2L: 70-75 g: 360-370 g: 0.5-0.8L: 3-4L;
adding tris (2- (epoxy-2-methoxy) ethoxy) amine, bisphenol A, epoxy chloropropane and tetrabutylammonium bromide into 1, 4-dioxane, stirring at 25-35 ℃ for at least 30 minutes, heating to 75-85 ℃, stirring for 1-2 hours, adding a sodium hydroxide solution, stirring for 6-8 hours, cooling to 20-30 ℃, standing for layering, washing an organic phase with water, distilling under reduced pressure to remove a solvent, and drying to obtain the hyperbranched epoxy resin;
the mass concentration of the sodium hydroxide solution is 18-22%;
wherein the mass volume ratio of the tri (2- (epoxy-2-methoxy) ethoxy) amine to the bisphenol A to the epichlorohydrin to the tetrabutylammonium bromide to the 1, 4-dioxane to the sodium hydroxide solution is 10-15 g: 220-230 g: 550-560 g: 30-35 g: 1.6-2.0L: 0.5-0.6L;
the diluent is an alcohol or ketone organic solvent;
the curing agent is an amine curing agent;
the flatting agent is polyether modified polydimethylsiloxane solution;
the filler is one or two of mica powder, talcum powder or hollow glass beads.
Preferably, the leveling agent is BYK-346 or BYK-333 from BYK, Germany.
Preferably, the amine curing agent is diethylenetriamine or triethylenetetramine.
Preferably, the dispersant is BYK-P104 or BYK-P105 from BYK, Germany.
Preferably, the filler is talcum powder and hollow glass beads according to a mass ratio of 1: 1.
Preferably, the filler is pretreated by a silane coupling agent, specifically:
adding a silane coupling agent into an ethanol water solution with the mass concentration of 70-75%, starting stirring, adding a filler into the ethanol water solution in several times, ultrasonically dispersing for 0.5-1 hour, then placing the mixture into an oven, and drying the mixture at the temperature of 95-100 ℃ to obtain a silane modified filler;
wherein the mass ratio of the silane coupling agent to the ethanol aqueous solution to the filler is 0.3-0.5: 100: 20-30;
the silane coupling agent is KH560 or KH 570.
Preferably, the diluent is ethanol, propanol or acetone.
The invention also discloses a preparation method of the hyperbranched modified epoxy resin finish paint with strong weather resistance, which comprises the following steps:
the composite material comprises the following raw materials in parts by weight: 55-65 parts of hyperbranched epoxy resin, 20-30 parts of diluent, 20-30 parts of filler, 5-8 parts of dispersant and 0.5-1 part of flatting agent are mixed and stirred uniformly, the mixture is ground until the fineness is less than 50 microns, 15-25 parts of curing agent is added under the protection of nitrogen, the mixture is stirred for 20-30 minutes and mixed uniformly, and the hyperbranched modified epoxy resin finish paint with strong weather resistance is obtained;
the hyperbranched epoxy resin is prepared by the following steps:
dissolving triethanolamine in N, N-dimethylformamide, stirring, cooling to 0-5 ℃, adding sodium hydride, stirring for 10 minutes, adding epoxy chloropropane at the temperature, stirring for at least 30 minutes, heating to 20-25 ℃, stirring for reaction for 2-3 hours, adding distilled water, stirring for 30-40 minutes, adding ethyl acetate, stirring for 20-30 minutes, standing for layering, adding water into an organic phase, extracting and washing, standing for layering, removing a solvent by virtue of vacuum distillation of the organic phase, and recrystallizing the obtained solid with methanol to obtain tris (2- (epoxy-2-methoxy) ethoxy) amine;
wherein the mass volume ratio of the trihydroxyethylamine to the N, N-dimethylformamide to the sodium hydride to the epichlorohydrin to the distilled water to the ethyl acetate is 140-150 g: 1.5-2L: 70-75 g: 360-370 g: 0.5-0.8L: 3-4L;
adding tris (2- (epoxy-2-methoxy) ethoxy) amine, bisphenol A, epoxy chloropropane and tetrabutylammonium bromide into 1, 4-dioxane, stirring at 25-35 ℃ for at least 30 minutes, heating to 75-85 ℃, stirring for 1-2 hours, adding a sodium hydroxide solution, stirring for 6-8 hours, cooling to 20-30 ℃, standing for layering, washing an organic phase with water, distilling under reduced pressure to remove a solvent, and drying to obtain the hyperbranched epoxy resin;
the mass concentration of the sodium hydroxide solution is 18-22%;
wherein the mass volume ratio of the tri (2- (epoxy-2-methoxy) ethoxy) amine to the bisphenol A to the epichlorohydrin to the tetrabutylammonium bromide to the 1, 4-dioxane to the sodium hydroxide solution is 10-15 g: 220-230 g: 550-560 g: 30-35 g: 1.6-2.0L: 0.5-0.6L;
the diluent is an alcohol or ketone organic solvent;
the curing agent is an amine curing agent;
the flatting agent is polyether modified polydimethylsiloxane solution;
the filler is one or two of mica powder, talcum powder or hollow glass beads.
Compared with the prior art, the invention has the following advantages:
the hyperbranched epoxy resin has high epoxy functionality, can form a paint film with high crosslinking density in finish paint, and has a structure containing a large amount of ether bonds obtained by epoxy resin and hydroxyl functional groups, so that the flexibility of the structure is improved, the viscosity of the obtained hyperbranched epoxy resin is low, the problem of high viscosity caused by the structure and molecular weight of the existing hyperbranched resin is solved, and the paint can be conveniently sprayed;
the hyperbranched modified epoxy resin finish paint with strong weather resistance has short surface drying time and actual drying time, the hardness of the paint film can reach 2-4H, the hardness is high, the adhesive force is 0-1 grade, the adhesive force is strong, the high-temperature water immersion resistance is high, the salt water resistance, the acid and alkali resistance and the weather resistance are excellent, and the hyperbranched modified epoxy resin finish paint is suitable for active popularization and application in the market.
The hyperbranched epoxy resin can be matched with conventional components in the market for use, so that the cost of additionally researching and developing matched fillers is reduced, and the synergistic effect among the materials is obvious; the hyperbranched modified epoxy resin finish paint with strong weather resistance provided by the invention takes hyperbranched epoxy resin as a base material and can improve the crosslinking density of a coating, increase the hardness and adhesive force of a paint film and improve the flexibility and aging resistance of the paint film.
Detailed Description
The invention aims to provide a hyperbranched modified epoxy resin finish with strong weather resistance and a preparation method thereof, and the hyperbranched modified epoxy resin finish is realized by the following technical scheme:
a hyperbranched modified epoxy resin finish paint with strong weather resistance is composed of the following raw materials in parts by weight: 55-65 parts of hyperbranched epoxy resin, 20-30 parts of diluent, 20-30 parts of filler, 5-8 parts of dispersing agent, 15-25 parts of curing agent and 0.5-1 part of flatting agent;
the hyperbranched epoxy resin is prepared by the following steps:
dissolving triethanolamine in N, N-dimethylformamide, stirring, cooling to 0-5 ℃, adding sodium hydride, stirring for 10 minutes, adding epoxy chloropropane at the temperature, stirring for at least 30 minutes, heating to 20-25 ℃, stirring for reaction for 2-3 hours, adding distilled water, stirring for 30-40 minutes, adding ethyl acetate, stirring for 20-30 minutes, standing for layering, adding water into an organic phase, extracting and washing, standing for layering, removing a solvent by virtue of vacuum distillation of the organic phase, and recrystallizing the obtained solid with methanol to obtain tris (2- (epoxy-2-methoxy) ethoxy) amine;
wherein the mass volume ratio of the trihydroxyethylamine to the N, N-dimethylformamide to the sodium hydride to the epichlorohydrin to the distilled water to the ethyl acetate is 140-150 g: 1.5-2L: 70-75 g: 360-370 g: 0.5-0.8L: 3-4L;
adding tris (2- (epoxy-2-methoxy) ethoxy) amine, bisphenol A, epoxy chloropropane and tetrabutylammonium bromide into 1, 4-dioxane, stirring at 25-35 ℃ for at least 30 minutes, heating to 75-85 ℃, stirring for 1-2 hours, adding a sodium hydroxide solution, stirring for 6-8 hours, cooling to 20-30 ℃, standing for layering, washing an organic phase with water, distilling under reduced pressure to remove a solvent, and drying to obtain the hyperbranched epoxy resin;
the mass concentration of the sodium hydroxide solution is 18-22%;
wherein the mass volume ratio of the tri (2- (epoxy-2-methoxy) ethoxy) amine to the bisphenol A to the epichlorohydrin to the tetrabutylammonium bromide to the 1, 4-dioxane to the sodium hydroxide solution is 10-15 g: 220-230 g: 550-560 g: 30-35 g: 1.6-2.0L: 0.5-0.6L;
the hyperbranched epoxy resin of the invention firstly adopts the reaction of the triethanolamine and the excessive epichlorohydrin to obtain the compound 1 tris (2- (epoxy-2-methoxy) ethoxy) amine, then the compound 1 reacts with the excessive bisphenol A and the excessive epichlorohydrin to obtain the hyperbranched epoxy resin, the hyperbranched structure comprises three epoxy group ring-opening on the compound 1 which firstly reacts with one hydroxyl group on the bisphenol A, then the other hydroxyl group on the bisphenol A reacts with a branched chain of the epichlorohydrin, and also comprises three epoxy group ring-opening on the compound 1 which firstly reacts with one hydroxyl group on the bisphenol A, then the other hydroxyl group on the bisphenol A reacts with the branched chain of the other epoxy group on the compound 1, or the hydroxyl group on the bisphenol A firstly reacts with the chlorine on the epichlorohydrin, then the epoxy group reacts with the hydroxyl group on the other bisphenol A molecules, then, the analogy is carried out, and the dendritic hyperbranched epoxy resin is obtained; the reaction principle equation is as follows:
the diluent is an alcohol or ketone organic solvent;
the curing agent is an amine curing agent;
the flatting agent is polyether modified polydimethylsiloxane solution;
the filler is one or two of mica powder, talcum powder or hollow glass beads.
The hyperbranched epoxy resin has high epoxy functionality, and the structure contains a large amount of ether bonds obtained by epoxy resin and hydroxyl functional groups, so that the flexibility of the structure is improved, the viscosity of the obtained hyperbranched epoxy resin is low, the problem of high viscosity caused by the structure and molecular weight of the existing hyperbranched resin is solved, and the paint is convenient to spray; the hyperbranched epoxy resin can be matched with conventional components in the market for use, so that the cost of additionally researching and developing matched fillers is reduced, and the synergistic effect among the materials is obvious; the hyperbranched modified epoxy resin finish paint with strong weather resistance provided by the invention takes hyperbranched epoxy resin as a base material and can improve the crosslinking density of a coating, increase the hardness and adhesive force of a paint film and improve the flexibility and aging resistance of the paint film.
Preferably, the leveling agent is BYK-346 or BYK-333 from BYK, Germany.
Preferably, the amine curing agent is diethylenetriamine or triethylenetetramine.
Preferably, the dispersant is BYK-P104 or BYK-P105 from BYK, Germany.
Preferably, the filler is talcum powder and hollow glass beads according to a mass ratio of 1: 1.
Preferably, the filler is pretreated by a silane coupling agent, specifically:
adding a silane coupling agent into an ethanol water solution with the mass concentration of 70-75%, starting stirring, adding a filler into the ethanol water solution in several times, ultrasonically dispersing for 0.5-1 hour, then placing the mixture into an oven, and drying the mixture at the temperature of 95-100 ℃ to obtain a silane modified filler;
wherein the mass ratio of the silane coupling agent to the ethanol aqueous solution to the filler is 0.3-0.5: 100: 20-30;
the silane coupling agent is KH560 or KH 570.
The preferable filler treated by the silane coupling agent has the advantages that alkoxy in the silane coupling agent is hydrolyzed to form silanol, and the silanol can react with hydroxyl on the surface of the filler and other structures to form covalent bonds, so that the dispersibility of the filler is improved, and the heat insulation performance, the weather resistance performance and other performances of the coating are improved.
Preferably, the diluent is ethanol, propanol or acetone.
The invention also discloses a preparation method of the hyperbranched modified epoxy resin finish paint with strong weather resistance, which comprises the following steps:
the composite material comprises the following raw materials in parts by weight: 55-65 parts of hyperbranched epoxy resin, 20-30 parts of diluent, 20-30 parts of filler, 5-8 parts of dispersant and 0.5-1 part of flatting agent are mixed and stirred uniformly, the mixture is ground until the fineness is less than 50 microns, 15-25 parts of curing agent is added under the protection of nitrogen, the mixture is stirred for 20-30 minutes and mixed uniformly, and the hyperbranched modified epoxy resin finish paint with strong weather resistance is obtained;
the hyperbranched epoxy resin is prepared by the following steps:
dissolving triethanolamine in N, N-dimethylformamide, stirring, cooling to 0-5 ℃, adding sodium hydride, stirring for 10 minutes, adding epoxy chloropropane at the temperature, stirring for at least 30 minutes, heating to 20-25 ℃, stirring for reaction for 2-3 hours, adding distilled water, stirring for 30-40 minutes, adding ethyl acetate, stirring for 20-30 minutes, standing for layering, adding water into an organic phase, extracting and washing, standing for layering, removing a solvent by virtue of vacuum distillation of the organic phase, and recrystallizing the obtained solid with methanol to obtain tris (2- (epoxy-2-methoxy) ethoxy) amine;
wherein the mass volume ratio of the trihydroxyethylamine to the N, N-dimethylformamide to the sodium hydride to the epichlorohydrin to the distilled water to the ethyl acetate is 140-150 g: 1.5-2L: 70-75 g: 360-370 g: 0.5-0.8L: 3-4L;
adding tris (2- (epoxy-2-methoxy) ethoxy) amine, bisphenol A, epoxy chloropropane and tetrabutylammonium bromide into 1, 4-dioxane, stirring at 25-35 ℃ for at least 30 minutes, heating to 75-85 ℃, stirring for 1-2 hours, adding a sodium hydroxide solution, stirring for 6-8 hours, cooling to 20-30 ℃, standing for layering, washing an organic phase with water, distilling under reduced pressure to remove a solvent, and drying to obtain the hyperbranched epoxy resin;
the mass concentration of the sodium hydroxide solution is 18-22%;
wherein the mass volume ratio of the tri (2- (epoxy-2-methoxy) ethoxy) amine to the bisphenol A to the epichlorohydrin to the tetrabutylammonium bromide to the 1, 4-dioxane to the sodium hydroxide solution is 10-15 g: 220-230 g: 550-560 g: 30-35 g: 1.6-2.0L: 0.5-0.6L;
the diluent is an alcohol or ketone organic solvent;
the curing agent is an amine curing agent;
the flatting agent is polyether modified polydimethylsiloxane solution;
the filler is one or two of mica powder, talcum powder or hollow glass beads.
The organic solvent selected in the preparation process of the hyperbranched epoxy resin can be recycled and reused.
The invention is further described with reference to specific examples.
Example 1
A hyperbranched modified epoxy resin finish paint with strong weather resistance is composed of the following raw materials: 55kg of hyperbranched epoxy resin, 30kg of diluent, 20kg of filler, 5kg of dispersant, 15kg of curing agent and 1kg of flatting agent;
the hyperbranched epoxy resin is prepared by the following steps:
dissolving 1.4kg of triethanolamine in 15L N, N-dimethylformamide, stirring, cooling to 0-5 ℃, adding 0.7kg of sodium hydride in portions, stirring for 10 minutes, adding 3.6kg of epoxy chloropropane at the temperature, stirring for at least 30 minutes, heating to 20-25 ℃, stirring for reacting for 2-3 hours, adding 5L of distilled water, stirring for 30-40 minutes, adding 30L of ethyl acetate, stirring for 20-30 minutes, standing for layering, adding 2L of water into an organic phase, extracting and washing, standing for layering, removing the solvent by vacuum distillation of the organic phase, and recrystallizing the obtained solid with methanol to obtain tris (2- (epoxy-2-methoxy) ethoxy) amine;
adding 2.5kg of tris (2- (epoxy-2-methoxy) ethoxy) amine, 55kg of bisphenol A, 137.5kg of epoxy chloropropane and 7.5kg of tetrabutylammonium bromide into 400L of 1, 4-dioxane, stirring at 25 ℃ for 30 minutes, heating to 75 ℃, stirring for 2 hours, adding 125L of sodium hydroxide solution in batches, stirring for 6 hours, cooling to 20-30 ℃, standing for layering, washing an organic phase with 20L of water, removing the solvent by reduced pressure distillation, and drying to obtain the hyperbranched epoxy resin;
the mass concentration of the sodium hydroxide solution is 18 percent;
the diluent is isobutanol;
the curing agent is ethylenediamine;
the leveling agent is BYK-346 of Germany BYK company;
the filler is hollow glass beads.
The preparation method of the hyperbranched modified epoxy resin finish paint with strong weather resistance comprises the following steps:
55kg of hyperbranched epoxy resin, 30kg of diluent, 20kg of filler, 5kg of dispersant and 1kg of flatting agent are mixed and stirred uniformly, the mixture is ground until the fineness is less than 50 mu m, 15kg of curing agent is added under the protection of nitrogen, and the mixture is stirred for 20-30 minutes and mixed uniformly to obtain the hyperbranched modified epoxy resin finish paint with strong weather resistance.
Example 2
A hyperbranched modified epoxy resin finish paint with strong weather resistance is composed of the following raw materials: 65kg of hyperbranched epoxy resin, 20kg of diluent, 30kg of filler, 8kg of dispersant, 25kg of curing agent and 0.5kg of flatting agent;
the hyperbranched epoxy resin is prepared by the following steps:
dissolving 1.5kg of triethanolamine in 20L N, N-dimethylformamide, stirring, cooling to 0-5 ℃, adding 0.75kg of sodium hydride, stirring for 10 minutes, adding 3.7kg of epoxy chloropropane at the temperature, stirring for 40 minutes, heating to 20-25 ℃, stirring for reacting for 2.5 hours, adding 8L of distilled water, stirring for 40 minutes, adding 40L of ethyl acetate, stirring for 30 minutes, standing for layering, adding water into an organic phase, extracting and washing, standing for layering, removing the solvent by vacuum distillation of the organic phase, and recrystallizing the obtained solid with methanol to obtain tris (2- (epoxy-2-methoxy) ethoxy) amine;
adding 1.5kg of tris (2- (epoxy-2-methoxy) ethoxy) amine, 23kg of bisphenol A, 56kg of epoxy chloropropane and 3.5kg of tetrabutylammonium bromide into 200L of 1, 4-dioxane, stirring at 35 ℃ for at least 30 minutes, heating to 85 ℃, stirring for 2 hours, adding 60L of sodium hydroxide solution in batches, stirring for 8 hours, cooling to 30 ℃, standing for layering, washing an organic phase with 40L of water, distilling under reduced pressure to remove a solvent, and drying to obtain the hyperbranched epoxy resin;
the mass concentration of the sodium hydroxide solution is 22%;
the diluent is propanol;
the curing agent is diethylenetriamine;
the leveling agent is BYK-333 of Germany BYK company;
the filler is mica powder.
The preparation method of the hyperbranched modified epoxy resin finish paint with strong weather resistance comprises the following steps:
65kg of hyperbranched epoxy resin, 20kg of diluent, 30kg of filler, 8kg of dispersant and 0.5kg of flatting agent are mixed and stirred uniformly, the mixture is ground until the fineness is less than 50 mu m, 25kg of curing agent is added under the protection of nitrogen, and the mixture is stirred for 20-30 minutes and mixed uniformly to obtain the hyperbranched modified epoxy resin finish paint with strong weather resistance.
Example 3
A hyperbranched modified epoxy resin finish paint with strong weather resistance is composed of the following raw materials: 58kg of hyperbranched epoxy resin, 24kg of diluent, 26kg of filler, 7kg of dispersant, 18kg of curing agent and 0.6kg of flatting agent;
the hyperbranched epoxy resin is prepared by the following steps:
dissolving 1.42kg of triethanolamine in 16L N, N-dimethylformamide, stirring, cooling to 0-5 ℃, adding 0.72kg of sodium hydride, stirring for 10 minutes, adding 3.65kg of epoxy chloropropane at the temperature, stirring for at least 30 minutes, heating to 20-25 ℃, stirring for reacting for 2-3 hours, adding 6L of distilled water, stirring for 30-40 minutes, adding 32L of ethyl acetate, stirring for 20-30 minutes, standing for layering, adding water into an organic phase, extracting and washing, standing for layering, removing the solvent by vacuum distillation of the organic phase, and recrystallizing the obtained solid with methanol to obtain tris (2- (epoxy-2-methoxy) ethoxy) amine;
adding 1.2kg of tris (2- (epoxy-2-methoxy) ethoxy) amine, 22.2kg of bisphenol A, 55.2kg of epoxy chloropropane and 3.4kg of tetrabutylammonium bromide into 170L of 1, 4-dioxane, stirring for at least 30 minutes at 25-35 ℃, heating to 75-85 ℃, stirring for 1-2 hours, adding 55L of sodium hydroxide solution in batches, stirring for 6-8 hours, cooling to 20-30 ℃, standing for layering, washing an organic phase with 20L of water, distilling under reduced pressure to remove a solvent, and drying to obtain the hyperbranched epoxy resin;
the mass concentration of the sodium hydroxide solution is 20%;
the diluent is acetone;
the curing agent is triethylene tetramine;
the leveling agent is BYK-346 of Germany BYK company;
the filler is talcum powder.
The preparation method of the hyperbranched modified epoxy resin finish paint with strong weather resistance comprises the following steps:
and (2) uniformly mixing and stirring 58kg of hyperbranched epoxy resin, 24kg of diluent, 26kg of filler, 7kg of dispersant and 0.6kg of flatting agent, grinding until the fineness is less than 50 mu m, adding 18kg of curing agent under the protection of nitrogen, stirring for 20-30 minutes, and uniformly mixing to obtain the hyperbranched modified epoxy resin finish paint with strong weather resistance.
Example 4
A hyperbranched modified epoxy resin finish paint with strong weather resistance is composed of the following raw materials: 60kg of hyperbranched epoxy resin, 25kg of diluent, 28kg of filler, 6kg of dispersing agent, 20kg of curing agent and 0.8kg of flatting agent;
the hyperbranched epoxy resin is prepared by the following steps:
dissolving 1.48kg of triethanolamine in 18L N, N-dimethylformamide, stirring, cooling to 0-5 ℃, adding 0.74kg of sodium hydride, stirring for 10 minutes, adding 3.68kg of epoxy chloropropane at the temperature, stirring for at least 30 minutes, heating to 20-25 ℃, stirring for reacting for 2.5 hours, adding 6L of distilled water, stirring for 38 minutes, adding 38L of ethyl acetate, stirring for 28 minutes, standing for layering, adding water into an organic phase, extracting and washing, standing for layering, removing the solvent by vacuum distillation of the organic phase, and recrystallizing the obtained solid with methanol to obtain tris (2- (epoxy-2-methoxy) ethoxy) amine;
adding 1.4kg of tris (2- (epoxy-2-methoxy) ethoxy) amine, 22.5kg of bisphenol A, 55.5kg of epoxy chloropropane and 3.2kg of tetrabutylammonium bromide into 180L of 1, 4-dioxane, stirring at 30 ℃ for at least 30 minutes, heating to 80 ℃, stirring for 1.5 hours, adding 55L of sodium hydroxide solution in batches, stirring for 7 hours, cooling to 25 ℃, standing for layering, washing an organic phase with water, distilling under reduced pressure to remove a solvent, and drying to obtain the hyperbranched epoxy resin;
the mass concentration of the sodium hydroxide solution is 20%;
the diluent is propanol;
the curing agent is an amine curing agent;
the leveling agent is BYK-333 of Germany BYK company;
the filler is talcum powder and hollow glass beads according to a mass ratio of 1: 1.
The preparation method of the hyperbranched modified epoxy resin finish paint with strong weather resistance comprises the following steps:
60kg of hyperbranched epoxy resin, 25kg of diluent, 28kg of filler, 6kg of dispersant and 0.8kg of flatting agent are mixed and stirred uniformly, the mixture is ground until the fineness is less than 50 mu m, 20kg of curing agent is added under the protection of nitrogen, and the mixture is stirred for 20-30 minutes and mixed uniformly to obtain the hyperbranched modified epoxy resin finish paint with strong weather resistance.
Example 5
Except that the filler is pretreated by the silane coupling agent, the types and the proportions of the other components are the same as those of the embodiment 3;
the process of pretreating the filler by using a silane coupling agent comprises the following steps:
adding a silane coupling agent into an ethanol aqueous solution with the mass concentration of 70%, starting stirring, adding a filler talcum powder into the ethanol aqueous solution in several times, ultrasonically dispersing for 0.5 hour, then placing the filler talcum powder into an oven, and drying the filler talcum powder at the temperature of 95-100 ℃ to obtain a silane modified filler;
wherein the mass ratio of the silane coupling agent to the ethanol aqueous solution to the filler talc powder is 0.3: 100: 20;
the silane coupling agent is KH 560.
Example 6
The kinds and proportions of the remaining components were the same as in example 4 except that the filler was pretreated with a silane coupling agent.
The process of pretreating the filler by using a silane coupling agent comprises the following steps:
adding a silane coupling agent into an ethanol water solution with the mass concentration of 75%, starting stirring, adding a filler into the ethanol water solution in several times, ultrasonically dispersing for 1 hour, then placing the filler into an oven, and drying the filler at 95-100 ℃ to obtain a silane modified filler;
wherein the mass ratio of the silane coupling agent to the ethanol aqueous solution to the filler is 0.5: 100: 30, of a nitrogen-containing gas;
the silane coupling agent is KH 570;
the filler is talcum powder and hollow glass beads according to a mass ratio of 1: 1.
The viscosity of the hyperbranched modified epoxy resin finish paint with strong weather resistance in the embodiments 1-6 is measured on an NDJ-1 type rotational viscometer at 20 ℃, the viscosity range is 1700-1900 mPa.s, the viscosity is moderate, and the spraying is convenient. The paint films of the hyperbranched modified epoxy resin finish paints with strong weather resistance of the embodiments 1 to 6 are tested, and the results are shown in Table 1.
Wherein the surface drying time and the actual drying time are detected according to GB/T1728-79, the pencil hardness is detected according to GB/T6739-.
TABLE 1 paint film Property test standards and results Table
The results in table 1 show that the hyperbranched modified epoxy resin finish paint with strong weather resistance has short surface drying time and actual drying time, the hardness of the paint film can reach 2-4H, the hardness is high, the adhesive force is 0-1 grade, the adhesive force is strong, the high-temperature water immersion resistance, the salt water resistance, the acid and alkali resistance and the weather resistance are excellent, and the hyperbranched modified epoxy resin finish paint is suitable for active popularization and application in the market.
It can be seen from the comparative data of examples 4 to 7 that the filler treated by the silane coupling agent has better dispersibility, shorter surface drying time and actual drying time, higher hardness, and more excellent salt water resistance and acid resistance, because alkoxy in the silane coupling agent is hydrolyzed to form silanol which can react with structures such as hydroxyl on the surface of the filler to form covalent bonds, the dispersibility of the filler is improved, and the heat insulation and weather resistance of the coating are improved.
Claims (8)
1. A hyperbranched modified epoxy resin finish paint with strong weather resistance is characterized in that: the composite material comprises the following raw materials in parts by weight: 55-65 parts of hyperbranched epoxy resin, 20-30 parts of diluent, 20-30 parts of filler, 5-8 parts of dispersing agent, 15-25 parts of curing agent and 0.5-1 part of flatting agent;
the hyperbranched epoxy resin is prepared by the following steps:
dissolving triethanolamine in N, N-dimethylformamide, stirring, cooling to 0-5 ℃, adding sodium hydride, stirring for 10 minutes, adding epoxy chloropropane at the temperature, stirring for at least 30 minutes, heating to 20-25 ℃, stirring for reaction for 2-3 hours, adding distilled water, stirring for 30-40 minutes, adding ethyl acetate, stirring for 20-30 minutes, standing for layering, adding water into an organic phase, extracting and washing, standing for layering, removing a solvent by virtue of vacuum distillation of the organic phase, and recrystallizing the obtained solid with methanol to obtain tris (2- (epoxy-2-methoxy) ethoxy) amine;
wherein the mass volume ratio of the trihydroxyethylamine to the N, N-dimethylformamide to the sodium hydride to the epichlorohydrin to the distilled water to the ethyl acetate is 140-150 g: 1.5-2L: 70-75 g: 360-370 g: 0.5-0.8L: 3-4L;
adding tris (2- (epoxy-2-methoxy) ethoxy) amine, bisphenol A, epoxy chloropropane and tetrabutylammonium bromide into 1, 4-dioxane, stirring at 25-35 ℃ for at least 30 minutes, heating to 75-85 ℃, stirring for 1-2 hours, adding a sodium hydroxide solution, stirring for 6-8 hours, cooling to 20-30 ℃, standing for layering, washing an organic phase with water, distilling under reduced pressure to remove a solvent, and drying to obtain the hyperbranched epoxy resin;
the mass concentration of the sodium hydroxide solution is 18-22%;
wherein the mass volume ratio of the tri (2- (epoxy-2-methoxy) ethoxy) amine to the bisphenol A to the epichlorohydrin to the tetrabutylammonium bromide to the 1, 4-dioxane to the sodium hydroxide solution is 10-15 g: 220-230 g: 550-560 g: 30-35 g: 1.6-2.0L: 0.5-0.6L;
the diluent is an alcohol or ketone organic solvent;
the curing agent is an amine curing agent;
the flatting agent is polyether modified polydimethylsiloxane solution;
the filler is one or two of mica powder, talcum powder or hollow glass beads.
2. The hyperbranched modified epoxy resin finish paint with strong weather resistance of claim 1, which is characterized in that: the leveling agent is BYK-346 or BYK-333 of Germany BYK company.
3. The hyperbranched modified epoxy resin finish paint with strong weather resistance of claim 1, which is characterized in that: the amine curing agent is diethylenetriamine or triethylene tetramine.
4. The hyperbranched modified epoxy resin finish paint with strong weather resistance of claim 1, which is characterized in that: the dispersant is BYK-P104 or BYK-P105 of BYK company of Germany.
5. The hyperbranched modified epoxy resin finish paint with strong weather resistance of claim 1, which is characterized in that: the filler is talcum powder and hollow glass beads according to a mass ratio of 1: 1.
6. The hyperbranched modified epoxy resin finish paint with strong weather resistance of claim 1, which is characterized in that: the filler is pretreated by a silane coupling agent, and specifically comprises the following steps:
adding a silane coupling agent into an ethanol water solution with the mass concentration of 70-75%, starting stirring, adding a filler into the ethanol water solution in several times, ultrasonically dispersing for 0.5-1 hour, then placing the mixture into an oven, and drying the mixture at the temperature of 95-100 ℃ to obtain a silane modified filler;
wherein the mass ratio of the silane coupling agent to the ethanol aqueous solution to the filler is 0.3-0.5: 100: 20-30;
the silane coupling agent is KH560 or KH 570.
7. The hyperbranched modified epoxy resin finish paint with strong weather resistance of claim 1, which is characterized in that: the diluent is ethanol, propanol or acetone.
8. The preparation method of the hyperbranched modified epoxy resin finish paint with strong weather resistance, which is disclosed by claim 1, is characterized by comprising the following steps: the method comprises the following steps:
55-65 parts of hyperbranched epoxy resin, 20-30 parts of diluent, 20-30 parts of filler, 5-8 parts of dispersant and 0.5-1 part of flatting agent are uniformly mixed and stirred, the mixture is ground until the fineness is less than 50 mu m, 15-25 parts of curing agent is added under the protection of nitrogen, and the mixture is uniformly stirred for 20-30 minutes to obtain hyperbranched modified epoxy resin finish paint with strong weather resistance;
the hyperbranched epoxy resin is prepared by the following steps:
dissolving triethanolamine in N, N-dimethylformamide, stirring, cooling to 0-5 ℃, adding sodium hydride, stirring for 10 minutes, adding epoxy chloropropane at the temperature, stirring for at least 30 minutes, heating to 20-25 ℃, stirring for reaction for 2-3 hours, adding distilled water, stirring for 30-40 minutes, adding ethyl acetate, stirring for 20-30 minutes, standing for layering, adding water into an organic phase, extracting and washing, standing for layering, removing a solvent by virtue of vacuum distillation of the organic phase, and recrystallizing the obtained solid with methanol to obtain tris (2- (epoxy-2-methoxy) ethoxy) amine;
wherein the mass volume ratio of the trihydroxyethylamine to the N, N-dimethylformamide to the sodium hydride to the epichlorohydrin to the distilled water to the ethyl acetate is 140-150 g: 1.5-2L: 70-75 g: 360-370 g: 0.5-0.8L: 3-4L;
adding tris (2- (epoxy-2-methoxy) ethoxy) amine, bisphenol A, epoxy chloropropane and tetrabutylammonium bromide into 1, 4-dioxane, stirring at 25-35 ℃ for at least 30 minutes, heating to 75-85 ℃, stirring for 1-2 hours, adding a sodium hydroxide solution, stirring for 6-8 hours, cooling to 20-30 ℃, standing for layering, washing an organic phase with water, distilling under reduced pressure to remove a solvent, and drying to obtain the hyperbranched epoxy resin;
the mass concentration of the sodium hydroxide solution is 18-22%;
wherein the mass volume ratio of the tri (2- (epoxy-2-methoxy) ethoxy) amine to the bisphenol A to the epichlorohydrin to the tetrabutylammonium bromide to the 1, 4-dioxane to the sodium hydroxide solution is 10-15 g: 220-230 g: 550-560 g: 30-35 g: 1.6-2.0L: 0.5-0.6L;
the diluent is an alcohol or ketone organic solvent;
the curing agent is an amine curing agent;
the flatting agent is polyether modified polydimethylsiloxane solution;
the filler is one or two of mica powder, talcum powder or hollow glass beads.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011571504.0A CN112708323A (en) | 2020-12-27 | 2020-12-27 | Hyperbranched modified epoxy resin finish paint with high weather resistance and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011571504.0A CN112708323A (en) | 2020-12-27 | 2020-12-27 | Hyperbranched modified epoxy resin finish paint with high weather resistance and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN112708323A true CN112708323A (en) | 2021-04-27 |
Family
ID=75545544
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202011571504.0A Pending CN112708323A (en) | 2020-12-27 | 2020-12-27 | Hyperbranched modified epoxy resin finish paint with high weather resistance and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN112708323A (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113151745A (en) * | 2021-05-08 | 2021-07-23 | 马鞍山钢铁股份有限公司 | Acid and alkali corrosion resistant aluminum-zinc plated pre-coated plate and manufacturing method thereof |
| CN114538861A (en) * | 2022-04-01 | 2022-05-27 | 常州华光建材科技有限公司 | Water-based epoxy resin modified cement mortar and preparation method thereof |
| CN114940852A (en) * | 2022-06-13 | 2022-08-26 | 江苏卓奇新材料科技有限公司 | Solvent-free epoxy coating and preparation method thereof |
| CN115011218A (en) * | 2022-07-01 | 2022-09-06 | 浙江维成新材料有限公司 | Solvent-free epoxy cabin coating |
| CN115651163A (en) * | 2022-11-14 | 2023-01-31 | 江苏扬农锦湖化工有限公司 | Hyperbranched epoxy resin and preparation method and application thereof |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101570592A (en) * | 2008-04-30 | 2009-11-04 | 北京化工大学 | Polyether type hyperbranched epoxy resin and preparation method thereof |
| CN102924690A (en) * | 2012-11-07 | 2013-02-13 | 北京化工大学 | Epoxy resin material used for toughening and reinforcing of hyperbranched polyether type epoxy resin and preparation method thereof |
| WO2013183721A1 (en) * | 2012-06-06 | 2013-12-12 | 日産化学工業株式会社 | Fluorine-containing hyperbranched polymer and epoxy resin composition containing same |
| CN104628995A (en) * | 2015-01-13 | 2015-05-20 | 廊坊立邦涂料有限公司 | Hyperbranched epoxy resin as well as preparation method and application thereof in coating |
| CN105925130A (en) * | 2016-05-23 | 2016-09-07 | 北京化工大学 | Hyper-branched polyether epoxy resin/epoxy resin composite anti-corrosion coating and preparation method thereof |
| CN111944120A (en) * | 2020-08-25 | 2020-11-17 | 江南大学 | Preparation method and application of low-viscosity polyether type hyperbranched epoxy resin |
-
2020
- 2020-12-27 CN CN202011571504.0A patent/CN112708323A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101570592A (en) * | 2008-04-30 | 2009-11-04 | 北京化工大学 | Polyether type hyperbranched epoxy resin and preparation method thereof |
| WO2013183721A1 (en) * | 2012-06-06 | 2013-12-12 | 日産化学工業株式会社 | Fluorine-containing hyperbranched polymer and epoxy resin composition containing same |
| CN102924690A (en) * | 2012-11-07 | 2013-02-13 | 北京化工大学 | Epoxy resin material used for toughening and reinforcing of hyperbranched polyether type epoxy resin and preparation method thereof |
| CN104628995A (en) * | 2015-01-13 | 2015-05-20 | 廊坊立邦涂料有限公司 | Hyperbranched epoxy resin as well as preparation method and application thereof in coating |
| CN105925130A (en) * | 2016-05-23 | 2016-09-07 | 北京化工大学 | Hyper-branched polyether epoxy resin/epoxy resin composite anti-corrosion coating and preparation method thereof |
| CN111944120A (en) * | 2020-08-25 | 2020-11-17 | 江南大学 | Preparation method and application of low-viscosity polyether type hyperbranched epoxy resin |
Non-Patent Citations (4)
| Title |
|---|
| M AHMARUZZAMAN等: "Environmental benign synthesis of low-viscous triethanolamine based hyper-branched epoxy thermoset", 《INDIAN JOURNAL OF CHEMICAL TECHNOLOGY》 * |
| MEHDI MAHMOUDIAN等: "Clay-hyperbranched epoxy/polyphenylsulfone nanocomposite membranes", 《IRAN POLYMER JOURNAL》 * |
| 章基凯: "《有机硅材料》", 31 October 1999, 中国物资出版社 * |
| 黄培强等: "《有机合成》", 28 February 2005, 高等教育出版社 * |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113151745A (en) * | 2021-05-08 | 2021-07-23 | 马鞍山钢铁股份有限公司 | Acid and alkali corrosion resistant aluminum-zinc plated pre-coated plate and manufacturing method thereof |
| CN114538861A (en) * | 2022-04-01 | 2022-05-27 | 常州华光建材科技有限公司 | Water-based epoxy resin modified cement mortar and preparation method thereof |
| CN114538861B (en) * | 2022-04-01 | 2022-12-13 | 常州华光建材科技有限公司 | Water-based epoxy resin modified cement mortar and preparation method thereof |
| CN114940852A (en) * | 2022-06-13 | 2022-08-26 | 江苏卓奇新材料科技有限公司 | Solvent-free epoxy coating and preparation method thereof |
| CN115011218A (en) * | 2022-07-01 | 2022-09-06 | 浙江维成新材料有限公司 | Solvent-free epoxy cabin coating |
| CN115651163A (en) * | 2022-11-14 | 2023-01-31 | 江苏扬农锦湖化工有限公司 | Hyperbranched epoxy resin and preparation method and application thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN112708323A (en) | Hyperbranched modified epoxy resin finish paint with high weather resistance and preparation method thereof | |
| CN110066383B (en) | Ionic waterborne epoxy curing agent and preparation method and application thereof | |
| CN108624194A (en) | Solventless epoxy coating, the corrosion-inhibiting coating based on its preparation and its application | |
| CN106928813B (en) | A kind of preparation method of the cross-linking aqueous epoxy coating of antibacterial colloidal sol | |
| KR101125845B1 (en) | SILICONE BASED TWO LIQUID TYPE ORGANIC·INORGANIC HYBRID COATINGS AND MANUFACTURAL METHODS | |
| CN112680072A (en) | Low-viscosity high-toughness quick-drying finish paint containing hyperbranched modified epoxy resin and preparation method thereof | |
| CN109851759B (en) | Organic silicon modified epoxy resin, preparation method thereof and organic silicon modified epoxy resin adhesive | |
| Gupta et al. | Development of siliconized epoxy resins and their application as anticorrosive coatings | |
| WO2016049832A1 (en) | Epoxy composition | |
| CN110386907B (en) | Epoxy resin monomer containing imine bond, and preparation method and application thereof | |
| CN101696263A (en) | Epoxy resin curing agent, method for preparing same and application thereof | |
| EP3353227A1 (en) | Epoxy terminated butadiene and butadiene acrylonitrile copolymers | |
| CN111303729B (en) | Solvent-free anticorrosive paint and preparation method thereof | |
| CN110511356A (en) | A kind of silicon oil modified aqueous epoxy curing agent of epoxy and phenyl and preparation method thereof | |
| CN114181589A (en) | High-salt-spray-resistance water-based tower barrel coating and preparation method thereof | |
| CN106939138B (en) | A kind of preparation method of antistripping oligomer waterborne epoxy coatings | |
| Guangqi et al. | Synthesis and characterization of waterborne epoxy curing agent modified by silane | |
| CN1247652C (en) | Epoxy resin containing double bonds and curing system | |
| CN111607105A (en) | Bio-based epoxy resin emulsifier, water-based emulsion thereof and preparation method | |
| CN114437657B (en) | Preparation method of high-strength metal epoxy AB glue | |
| JP2002338787A (en) | Epoxy resin composition and its cured product | |
| CN112961350B (en) | High-temperature-resistant resin, preparation method and application thereof, high-temperature-resistant coating containing high-temperature-resistant resin, preparation method and coating | |
| CN110982385B (en) | Special temperature-resistant coating for corrosion prevention in heat storage tank | |
| CN114349935A (en) | Low-viscosity water-based epoxy curing agent and preparation method thereof | |
| CN113621298A (en) | Water-based epoxy resin for high-corrosion-resistance weather-resistant paint and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20210427 |