CN112680072A - Low-viscosity high-toughness quick-drying finish paint containing hyperbranched modified epoxy resin and preparation method thereof - Google Patents
Low-viscosity high-toughness quick-drying finish paint containing hyperbranched modified epoxy resin and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a low-viscosity high-toughness quick-drying finish paint containing hyperbranched modified epoxy resin and a preparation method thereof, and the finish paint comprises the following raw materials in parts by weight: 45-55 parts of hyperbranched modified epoxy resin, 20-30 parts of diluent, 20-30 parts of filler, 5-10 parts of dispersant, 20-30 parts of curing agent and 1-2 parts of toughening agent; the hyperbranched modified epoxy resin has ingenious structural design, can form a paint film with high crosslinking density in the finish paint, on one hand, the structure contains a large number of ether bonds obtained by epoxy resin and hydroxyl functional groups, so that the structural flexibility of the hyperbranched modified epoxy resin is increased, and the viscosity of the hyperbranched modified epoxy resin is low.
Description
Technical Field
The invention relates to the technical field of high polymer materials and coatings, in particular to a low-viscosity high-toughness quick-drying finish paint containing hyperbranched modified epoxy resin and a preparation method thereof.
Background
The hyperbranched polymer is a highly regular branched macromolecule with a three-dimensional branched structure, the molecular structure has a symmetrical long-chain structure, is similar to a sphere, has small hydrodynamic radius of gyration, high branching degree and less molecular chain entanglement, so the relation between viscosity and molecular weight is not large, and the viscosity can not change rapidly along with relative molecular weight, and provides possibility for preparing low-viscosity paint theoretically.
Epoxy resin is a high molecular compound containing epoxy groups in a molecular structure, and the cured epoxy resin has good physical and chemical properties and excellent bonding viscosity on the surfaces of metal and nonmetal materials, so the epoxy resin is widely applied to various departments of national defense and national economy, but the hyperbranched epoxy resin is slower in development for the following reasons:
firstly, the functionality of epoxy resin in the 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, because the existing hyperbranched epoxy resin compound has unreasonable structural design, high hydroxyl functionality and strong polarity, strong hydrogen bonds are easily formed among molecules, and the compound is easy to agglomerate and can not be effectively dispersed in the coating.
Disclosure of Invention
In order to solve the problem that the existing hyperbranched epoxy resin is slow in development and cannot meet the market demand, the invention aims to provide a low-viscosity high-toughness quick-drying finish paint containing hyperbranched modified epoxy resin and a preparation method thereof.
In order to achieve the purpose, the invention is realized by the following technical scheme:
a low-viscosity high-toughness quick-drying finish paint containing hyperbranched modified epoxy resin comprises the following raw materials in parts by weight: 45-55 parts of hyperbranched modified epoxy resin, 20-30 parts of diluent, 20-30 parts of filler, 5-10 parts of dispersant, 20-30 parts of curing agent and 1-2 parts of toughening agent;
the hyperbranched modified epoxy resin is prepared by the following steps:
dissolving triethanolamine in N, N-dimethylformamide, stirring and cooling to 0-5 ℃, adding sodium hydride at the temperature, stirring for 10-15 minutes, adding 4-fluorobenzaldehyde, stirring for 1-2 hours, adding water, stirring for at least 30 minutes, adding ethyl acetate, stirring for 20-30 minutes, standing and layering, adding an organic phase, washing with water in an amount equal to that of the previous time, stirring for at least 10 minutes, standing and layering, removing the solvent by vacuum distillation of the organic phase, and recrystallizing the obtained solid with methanol to obtain a compound 1;
wherein the mass volume ratio of the trihydroxyethylamine to the N, N-dimethylformamide to the sodium hydride to the 4-fluorobenzaldehyde to the water to the ethyl acetate to the methanol is 145-155 g: 1-1.5L: 70-80 g: 495-505 g: 0.4-0.5L: 2-3L: 1.5-2.5L;
dissolving the compound 1 obtained in the step I in methanol, cooling to 0-5 ℃ by stirring, adding sodium borohydride in three batches, stirring for at least half an hour after each addition, adding the next batch, ensuring the temperature to be 0-5 ℃, stirring for at least half an hour after the last addition, heating to 20-30 ℃, stirring for 1 hour, adding water, stirring for 30 minutes, distilling under reduced pressure to remove the solvent, adding ethyl acetate, washing with water successively, adding petroleum ether, stirring for at least 6 hours until white solids are separated out, filtering, and drying a filter cake under reduced pressure to obtain a compound 2; in the step, the water adding amount in two times is the same;
the mass-to-volume ratio of the compound 1, methanol, sodium borohydride, water, ethyl acetate and petroleum ether obtained in the step (i) is 460-470 g: 2-2.5L: 120-130 g: 0.5-0.6L: 0.8-0.9L: 2-2.5L;
dissolving the compound 2 obtained in the step II in N, N-dimethylformamide, stirring and cooling to 0-5 ℃, adding sodium hydride, stirring and reacting for at least 10 minutes, adding epoxy chloropropane, stirring for at least 30 minutes, heating to 20-25 ℃, stirring and reacting for 4-5 hours, adding water, stirring for at least 30 minutes, adding ethyl acetate, stirring for 20 minutes, standing and layering, adding water into an organic phase, stirring for 10 minutes, standing and layering, removing the solvent by vacuum distillation of the organic phase, and recrystallizing the obtained solid with a mixed solvent to obtain a compound 3; in the step, the water adding amount in two times is the same;
the mixed solvent is petroleum ether and ethyl acetate according to the volume ratio of 1: 1, mixing to obtain;
wherein the mass-to-volume ratio of the compound 2 obtained in the second step, N-dimethylformamide, sodium hydride, epichlorohydrin, water, ethyl acetate and mixed solvent is 460-470 g: 2-3L: 75-85 g: 365-375 g: 2-3L: 4-5L: 3-4L;
adding the compound 3, the bisphenol A, the epoxy chloropropane and the tetrabutylammonium bromide obtained in the step (III) into dioxane, stirring for 30 minutes at the temperature of 20-30 ℃, heating to 70-80 ℃, stirring for 1 hour, adding a sodium hydroxide aqueous solution at the temperature of 70-80 ℃ in several times, stirring for reacting for 6-8 hours, cooling to 20-30 ℃, standing for layering, washing an organic phase with water, and distilling under reduced pressure to remove a solvent to obtain the hyperbranched modified epoxy resin;
wherein the mass volume ratio of the compound 3, bisphenol A, epoxy chloropropane, tetrabutylammonium bromide, dioxane, sodium hydroxide aqueous solution and water obtained in the step (III) is 25-35 g: 225-235 g: 715-725 g: 30-40 g: 2-2.5L: 0.65-0.7L: 2-3L;
the mass concentration of the sodium hydroxide aqueous solution is 20-25%;
the diluent is dioxane or an ester solvent;
the curing agent is an amine curing agent;
the toughening agent is phthalate;
the filler is one or two of calcium carbonate, quartz powder or attapulgite.
Preferably, the ester solvent is methyl acetate, butyl acetate or ethyl acetate.
Preferably, the amine curing agent is diethylenetriamine or hexamethylenediamine.
Preferably, the toughening agent is dimethyl phthalate or dibutyl phthalate.
Preferably, the dispersant is an epoxy dispersant CM-3191, BYK-P104 or BYK-P105 from BYK, Germany.
Preferably, the filler is treated by a silane coupling agent, and the process is as follows:
firing the filler at 500-600 ℃ for at least 1 hour, and carrying out activation pretreatment for later use;
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 filler is one or two of calcium carbonate, quartz powder or attapulgite.
The invention also discloses a preparation method of the low-viscosity high-toughness quick-drying finish paint containing the hyperbranched modified epoxy resin, which comprises the following steps:
according to parts by weight, uniformly mixing 45-55 parts of hyperbranched modified epoxy resin, 20-30 parts of diluent, 20-30 parts of filler, 5-10 parts of dispersant and 1-2 parts of toughening agent, grinding until the fineness is less than 50 microns, adding 20-30 parts of curing agent under the protection of nitrogen, stirring for 20-30 minutes, and uniformly mixing to obtain the low-viscosity high-toughness quick-drying finish paint containing the hyperbranched modified epoxy resin;
the hyperbranched modified epoxy resin is prepared by the following steps:
dissolving triethanolamine in N, N-dimethylformamide, stirring and cooling to 0-5 ℃, adding sodium hydride at the temperature, stirring for 10-15 minutes, adding 4-fluorobenzaldehyde, stirring for 1-2 hours, adding water, stirring for at least 30 minutes, adding ethyl acetate, stirring for 20-30 minutes, standing and layering, adding an organic phase, washing with water in an amount equal to that of the previous time, stirring for at least 10 minutes, standing and layering, removing the solvent by vacuum distillation of the organic phase, and recrystallizing the obtained solid with methanol to obtain a compound 1;
wherein the mass volume ratio of the trihydroxyethylamine to the N, N-dimethylformamide to the sodium hydride to the 4-fluorobenzaldehyde to the water to the ethyl acetate to the methanol is 145-155 g: 1-1.5L: 70-80 g: 495-505 g: 0.4-0.5L: 2-3L: 1.5-2.5L;
dissolving the compound 1 obtained in the step I in methanol, cooling to 0-5 ℃ by stirring, adding sodium borohydride in three batches, stirring for at least half an hour after each addition, adding the next batch, ensuring the temperature to be 0-5 ℃, stirring for at least half an hour after the last addition, heating to 20-30 ℃, stirring for 1 hour, adding water, stirring for 30 minutes, distilling under reduced pressure to remove the solvent, adding ethyl acetate, washing with water successively, adding petroleum ether, stirring for at least 6 hours until white solids are separated out, filtering, and drying a filter cake under reduced pressure to obtain a compound 2; in the step, the water adding amount in two times is the same;
the mass-to-volume ratio of the compound 1, methanol, sodium borohydride, water, ethyl acetate and petroleum ether obtained in the step (i) is 460-470 g: 2-2.5L: 120-130 g: 0.5-0.6L: 0.8-0.9L: 2-2.5L;
dissolving the compound 2 obtained in the step II in N, N-dimethylformamide, stirring and cooling to 0-5 ℃, adding sodium hydride, stirring and reacting for at least 10 minutes, adding epoxy chloropropane, stirring for at least 30 minutes, heating to 20-25 ℃, stirring and reacting for 4-5 hours, adding water, stirring for at least 30 minutes, adding ethyl acetate, stirring for 20 minutes, standing and layering, adding water into an organic phase, stirring for 10 minutes, standing and layering, removing the solvent by vacuum distillation of the organic phase, and recrystallizing the obtained solid with a mixed solvent to obtain a compound 3; in the step, the water adding amount in two times is the same;
the mixed solvent is petroleum ether and ethyl acetate according to the volume ratio of 1: 1, mixing to obtain;
wherein the mass-to-volume ratio of the compound 2 obtained in the second step, N-dimethylformamide, sodium hydride, epichlorohydrin, water, ethyl acetate and mixed solvent is 460-470 g: 2-3L: 75-85 g: 365-375 g: 2-3L: 4-5L: 3-4L;
adding the compound 3, the bisphenol A, the epoxy chloropropane and the tetrabutylammonium bromide obtained in the step (III) into dioxane, stirring for 30 minutes at the temperature of 20-30 ℃, heating to 70-80 ℃, stirring for 1 hour, adding a sodium hydroxide aqueous solution at the temperature of 70-80 ℃ in several times, stirring for reacting for 6-8 hours, cooling to 20-30 ℃, standing for layering, washing an organic phase with water, and distilling under reduced pressure to remove a solvent to obtain the hyperbranched modified epoxy resin;
wherein the mass volume ratio of the compound 3, bisphenol A, epoxy chloropropane, tetrabutylammonium bromide, dioxane, sodium hydroxide aqueous solution and water obtained in the step (III) is 25-35 g: 225-235 g: 715-725 g: 30-40 g: 2-2.5L: 0.65-0.7L: 2-3L;
the mass concentration of the sodium hydroxide aqueous solution is 20-25%;
the diluent is dioxane or an ester solvent;
the curing agent is an amine curing agent;
the toughening agent is phthalate;
the filler is one or two of calcium carbonate, quartz powder or attapulgite.
Compared with the prior art, the invention has the following advantages:
the hyperbranched modified epoxy resin has ingenious structural design, can form a paint film with high crosslinking density in a finish paint, on one hand, the structure contains a large number of ether bonds obtained by epoxy resin and hydroxyl functional groups, so that the structural flexibility of the hyperbranched modified epoxy resin is increased, and the viscosity of the hyperbranched modified epoxy resin is low;
the low-viscosity high-toughness quick-drying finish paint containing the hyperbranched modified epoxy resin has the advantages that firstly, the solubility of a polymer in the finish paint is good, the toughness is high, the molding property is good, and the film forming time is short, secondly, the compatibility of the base material hyperbranched modified epoxy resin and various auxiliary materials, such as a diluent, a filler, a dispersing agent, a curing agent and the like is good, all the auxiliary materials are conventional auxiliary materials on the market, the auxiliary materials matched with the base material are not required to be additionally researched and developed, the research and development cost is saved, the synergistic effect among the materials is obvious, for example, the diluent can improve the viscosity and the fluidity of the mixed materials, the curing process of the hyperbranched modified epoxy resin is activated, micropores cannot be generated after a paint film is cured, the; the filler has good thixotropy, can be well compatible with the hyperbranched modified epoxy resin, and can improve the weather resistance, acid and alkali resistance, corrosion resistance and mildew resistance of a paint film.
Detailed Description
The invention aims to provide a low-viscosity high-toughness quick-drying finish paint containing hyperbranched modified epoxy resin and a preparation method thereof, and the preparation method is realized by the following technical scheme:
a low-viscosity high-toughness quick-drying finish paint containing hyperbranched modified epoxy resin comprises the following raw materials in parts by weight: 45-55 parts of hyperbranched modified epoxy resin, 20-30 parts of diluent, 20-30 parts of filler, 5-10 parts of dispersant, 20-30 parts of curing agent and 1-2 parts of toughening agent;
the hyperbranched modified epoxy resin is prepared by the following steps:
dissolving triethanolamine in N, N-dimethylformamide, stirring and cooling to 0-5 ℃, adding sodium hydride at the temperature, stirring for 10-15 minutes, adding 4-fluorobenzaldehyde, stirring for 1-2 hours, adding water, stirring for at least 30 minutes, adding ethyl acetate, stirring for 20-30 minutes, standing and layering, adding an organic phase, washing with water in an amount equal to that of the previous time, stirring for at least 10 minutes, standing and layering, removing the solvent by vacuum distillation of the organic phase, and recrystallizing the obtained solid with methanol to obtain a compound 1;
wherein the mass volume ratio of the trihydroxyethylamine to the N, N-dimethylformamide to the sodium hydride to the 4-fluorobenzaldehyde to the water to the ethyl acetate to the methanol is 145-155 g: 1-1.5L: 70-80 g: 495-505 g: 0.4-0.5L: 2-3L: 1.5-2.5L;
dissolving the compound 1 obtained in the step I in methanol, cooling to 0-5 ℃ by stirring, adding sodium borohydride in three batches, stirring for at least half an hour after each addition, adding the next batch, ensuring the temperature to be 0-5 ℃, stirring for at least half an hour after the last addition, heating to 20-30 ℃, stirring for 1 hour, adding water, stirring for 30 minutes, distilling under reduced pressure to remove the solvent, adding ethyl acetate, washing with water successively, adding petroleum ether, stirring for at least 6 hours until white solids are separated out, filtering, and drying a filter cake under reduced pressure to obtain a compound 2; in the step, the water adding amount in two times is the same;
the mass-to-volume ratio of the compound 1, methanol, sodium borohydride, water, ethyl acetate and petroleum ether obtained in the step (i) is 460-470 g: 2-2.5L: 120-130 g: 0.5-0.6L: 0.8-0.9L: 2-2.5L;
dissolving the compound 2 obtained in the step II in N, N-dimethylformamide, stirring and cooling to 0-5 ℃, adding sodium hydride, stirring and reacting for at least 10 minutes, adding epoxy chloropropane, stirring for at least 30 minutes, heating to 20-25 ℃, stirring and reacting for 4-5 hours, adding water, stirring for at least 30 minutes, adding ethyl acetate, stirring for 20 minutes, standing and layering, adding water into an organic phase, stirring for 10 minutes, standing and layering, removing the solvent by vacuum distillation of the organic phase, and recrystallizing the obtained solid with a mixed solvent to obtain a compound 3; in the step, the water adding amount in two times is the same;
the mixed solvent is petroleum ether and ethyl acetate according to the volume ratio of 1: 1, mixing to obtain;
wherein the mass-to-volume ratio of the compound 2 obtained in the second step, N-dimethylformamide, sodium hydride, epichlorohydrin, water, ethyl acetate and mixed solvent is 460-470 g: 2-3L: 75-85 g: 365-375 g: 2-3L: 4-5L: 3-4L;
adding the compound 3, the bisphenol A, the epoxy chloropropane and the tetrabutylammonium bromide obtained in the step (III) into dioxane, stirring for 30 minutes at the temperature of 20-30 ℃, heating to 70-80 ℃, stirring for 1 hour, adding a sodium hydroxide aqueous solution at the temperature of 70-80 ℃ in several times, stirring for reacting for 6-8 hours, cooling to 20-30 ℃, standing for layering, washing an organic phase with water, and distilling under reduced pressure to remove a solvent to obtain the hyperbranched modified epoxy resin;
wherein the mass volume ratio of the compound 3, bisphenol A, epoxy chloropropane, tetrabutylammonium bromide, dioxane, sodium hydroxide aqueous solution and water obtained in the step (III) is 25-35 g: 225-235 g: 715-725 g: 30-40 g: 2-2.5L: 0.65-0.7L: 2-3L;
the mass concentration of the sodium hydroxide aqueous solution is 20-25%;
the hyperbranched modified epoxy resin of the invention firstly adopts trihydroxyethyl amine and 4-fluorobenzaldehyde in sodium hydride to obtain a compound 1, reduces aldehyde group on the compound 1 into hydroxyl group to obtain a compound 2, the compound 2 reacts with epoxy chloropropane to obtain a compound 3 containing epoxy group, the compound 3 reacts with excessive bisphenol A and epoxy chloropropane to obtain hyperbranched modified epoxy resin, the hyperbranched structure comprises three epoxy group open rings on the compound 3 which firstly react with one hydroxyl group on the bisphenol A, then the other hydroxyl group on the bisphenol A reacts with a branched chain of the epoxy chloropropane, and also comprises three epoxy group open rings on the compound 3 which firstly react with one hydroxyl group on the bisphenol A, then the other hydroxyl group on the bisphenol A reacts with another branched chain of the epoxy group on the compound 3, or the hydroxyl group on the bisphenol A reacts with chlorine on the epoxy chloropropane, then the epoxy group reacts with the hydroxyl on other bisphenol A molecules, and the like to obtain the dendritic hyperbranched modified epoxy resin; the principle reaction of the reaction is as follows:
the diluent is dioxane or an ester solvent;
the curing agent is an amine curing agent; the amine curing agent can be aliphatic amine or aromatic amine, preferably aliphatic amine, such as one or more of ethylenediamine, propylenediamine, diethylenetriamine, triethylenetetramine or hexamethylenediamine.
The toughening agent is phthalate, such as dimethyl phthalate, dibutyl phthalate, dioctyl phthalate, etc
The filler is one or two of calcium carbonate, quartz powder or attapulgite.
Preferably, the ester solvent is methyl acetate, butyl acetate or ethyl acetate.
Preferably, the amine curing agent is diethylenetriamine or hexamethylenediamine.
Preferably, the toughening agent is dimethyl phthalate or dibutyl phthalate.
Preferably, the dispersant is an epoxy dispersant CM-3191, BYK-P104 or BYK-P105 from BYK, Germany.
Preferably, the filler is treated by a silane coupling agent, and the process is as follows:
firing the filler at 500-600 ℃ for at least 1 hour, and carrying out activation pretreatment for later use, wherein the filler subjected to activation pretreatment has better dispersibility and is not easy to agglomerate during silane modification;
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 filler is one or two of calcium carbonate, quartz powder or attapulgite;
according to the preferable filler treated by the silane coupling agent, alkoxy in the silane coupling agent is hydrolyzed to form silanol which can react with hydroxyl on the surface of the activated and pretreated filler to form a covalent bond, so that the dispersibility of the filler is improved, and the performances of the coating, such as heat insulation, weather resistance and the like, are improved.
The invention also discloses a preparation method of the low-viscosity high-toughness quick-drying finish paint containing the hyperbranched modified epoxy resin, which comprises the following steps:
according to parts by weight, uniformly mixing 45-55 parts of hyperbranched modified epoxy resin, 20-30 parts of diluent, 20-30 parts of filler, 5-10 parts of dispersant and 1-2 parts of toughening agent, grinding until the fineness is less than 50 microns, adding 20-30 parts of curing agent under the protection of nitrogen, stirring for 20-30 minutes, and uniformly mixing to obtain the low-viscosity high-toughness quick-drying finish paint containing the hyperbranched modified epoxy resin;
the hyperbranched modified epoxy resin is prepared by the following steps:
dissolving triethanolamine in N, N-dimethylformamide, stirring and cooling to 0-5 ℃, adding sodium hydride at the temperature, stirring for 10-15 minutes, adding 4-fluorobenzaldehyde, stirring for 1-2 hours, adding water, stirring for at least 30 minutes, adding ethyl acetate, stirring for 20-30 minutes, standing and layering, adding an organic phase, washing with water in an amount equal to that of the previous time, stirring for at least 10 minutes, standing and layering, removing the solvent by vacuum distillation of the organic phase, and recrystallizing the obtained solid with methanol to obtain a compound 1;
wherein the mass volume ratio of the trihydroxyethylamine to the N, N-dimethylformamide to the sodium hydride to the 4-fluorobenzaldehyde to the water to the ethyl acetate to the methanol is 145-155 g: 1-1.5L: 70-80 g: 495-505 g: 0.4-0.5L: 2-3L: 1.5-2.5L;
dissolving the compound 1 obtained in the step I in methanol, cooling to 0-5 ℃ by stirring, adding sodium borohydride in three batches, stirring for at least half an hour after each addition, adding the next batch, ensuring the temperature to be 0-5 ℃, stirring for at least half an hour after the last addition, heating to 20-30 ℃, stirring for 1 hour, adding water, stirring for 30 minutes, distilling under reduced pressure to remove the solvent, adding ethyl acetate, washing with water successively, adding petroleum ether, stirring for at least 6 hours until white solids are separated out, filtering, and drying a filter cake under reduced pressure to obtain a compound 2; in the step, the water adding amount in two times is the same;
the mass-to-volume ratio of the compound 1, methanol, sodium borohydride, water, ethyl acetate and petroleum ether obtained in the step (i) is 460-470 g: 2-2.5L: 120-130 g: 0.5-0.6L: 0.8-0.9L: 2-2.5L;
dissolving the compound 2 obtained in the step II in N, N-dimethylformamide, stirring and cooling to 0-5 ℃, adding sodium hydride, stirring and reacting for at least 10 minutes, adding epoxy chloropropane, stirring for at least 30 minutes, heating to 20-25 ℃, stirring and reacting for 4-5 hours, adding water, stirring for at least 30 minutes, adding ethyl acetate, stirring for 20 minutes, standing and layering, adding water into an organic phase, stirring for 10 minutes, standing and layering, removing the solvent by vacuum distillation of the organic phase, and recrystallizing the obtained solid with a mixed solvent to obtain a compound 3; in the step, the water adding amount in two times is the same;
the mixed solvent is petroleum ether and ethyl acetate according to the volume ratio of 1: 1, mixing to obtain;
wherein the mass-to-volume ratio of the compound 2 obtained in the second step, N-dimethylformamide, sodium hydride, epichlorohydrin, water, ethyl acetate and mixed solvent is 460-470 g: 2-3L: 75-85 g: 365-375 g: 2-3L: 4-5L: 3-4L;
adding the compound 3, the bisphenol A, the epoxy chloropropane and the tetrabutylammonium bromide obtained in the step (III) into dioxane, stirring for 30 minutes at the temperature of 20-30 ℃, heating to 70-80 ℃, stirring for 1 hour, adding a sodium hydroxide aqueous solution at the temperature of 70-80 ℃ in several times, stirring for reacting for 6-8 hours, cooling to 20-30 ℃, standing for layering, washing an organic phase with water, and distilling under reduced pressure to remove a solvent to obtain the hyperbranched modified epoxy resin;
wherein the mass volume ratio of the compound 3, bisphenol A, epoxy chloropropane, tetrabutylammonium bromide, dioxane, sodium hydroxide aqueous solution and water obtained in the step (III) is 25-35 g: 225-235 g: 715-725 g: 30-40 g: 2-2.5L: 0.65-0.7L: 2-3L;
the mass concentration of the sodium hydroxide aqueous solution is 20-25%;
the diluent is dioxane or an ester solvent;
the curing agent is an amine curing agent;
the toughening agent is phthalate;
the filler is one or two of calcium carbonate, quartz powder or attapulgite.
The organic solvent selected in the preparation process of the hyperbranched modified epoxy resin can be recycled and reused.
The invention is further described with reference to specific examples.
Example 1
A low-viscosity and high-toughness quick-drying finish paint containing hyperbranched modified epoxy resin is composed of the following raw materials: 4.5kg of hyperbranched modified epoxy resin, 2kg of diluent, 2kg of filler, 0.5kg of dispersant, 2kg of curing agent and 0.1kg of toughening agent;
the hyperbranched modified epoxy resin is prepared by the following steps:
dissolving 1.45kg of triethanolamine in 10L N, N-dimethylformamide, stirring and cooling to 0-5 ℃, adding 0.7kg of sodium hydride at the temperature, stirring for 10 minutes, adding 4.95kg of 4-fluorobenzaldehyde, stirring for 1 hour, adding 4L of water, stirring for 35 minutes, adding 20L of ethyl acetate, stirring for 20 minutes, standing and layering, adding water which is the same as the previous washing to an organic phase, stirring for 15 minutes, standing and layering, removing the solvent by vacuum distillation of the organic phase, and recrystallizing the obtained solid with 15L of methanol to obtain a compound 1;
dissolving 2.3kg of the compound 1 obtained in the step I in 10L of methanol, stirring and cooling to 0-5 ℃, adding 0.6kg of sodium borohydride in three batches, stirring for at least half an hour after each addition, then adding the next batch, ensuring the temperature to be 0-5 ℃, stirring for 40 minutes after the last addition, heating to 22 ℃, stirring for 1 hour, adding 2.5L of water, stirring for 30 minutes, carrying out reduced pressure distillation to remove the solvent, adding 4L of ethyl acetate, continuously washing the organic phase with 2.5L of water, then adding 10L of petroleum ether, stirring for at least 6 hours until white solids are separated out, filtering, and drying the filter cake under reduced pressure to obtain a compound 2;
dissolving 2.3kg of the compound 2 obtained in the step II in 10L N, N-dimethylformamide, stirring and cooling to 0-5 ℃, adding 0.375kg of sodium hydride, stirring and reacting for 15 minutes, adding 1.825kg of epoxy chloropropane, stirring for 35 minutes, heating to 22 ℃, stirring and reacting for 4.2 hours, adding 10L of water, stirring for 35 minutes, adding 20L of ethyl acetate, stirring for 20 minutes, standing and layering, adding 10L of water into the organic phase, stirring for 10 minutes, standing and layering, removing the solvent by vacuum distillation of the organic phase, and recrystallizing the obtained solid with 15L of mixed solvent to obtain a compound 3;
the mixed solvent is petroleum ether and ethyl acetate according to the volume ratio of 1: 1, mixing to obtain;
adding 0.25kg of the compound 3 obtained in the step three, 2.25kg of bisphenol A, 7.15kg of epoxy chloropropane and 0.30kg of tetrabutylammonium bromide into 20L of dioxane, stirring at 22 ℃ for 30 minutes, heating to 70 ℃, stirring for 1 hour, adding 6.50L of sodium hydroxide aqueous solution at 70 ℃ in times, stirring for reacting for 6 hours, cooling to 20 ℃, standing for layering, washing the organic phase with 20L of water, and removing the solvent by reduced pressure distillation to obtain the hyperbranched modified epoxy resin;
the mass concentration of the sodium hydroxide aqueous solution is 20 percent;
the diluent is dioxane;
the curing agent is hexamethylene diamine;
the toughening agent is dimethyl phthalate;
the filler is calcium carbonate
The dispersant is an epoxy dispersant CM-3191.
The preparation method of the low-viscosity high-toughness quick-drying finish paint containing the hyperbranched modified epoxy resin comprises the following steps: 4.5kg of hyperbranched modified epoxy resin, 2kg of diluent, 2kg of filler, 0.5kg of dispersant and 0.1kg of toughening agent are mixed and stirred uniformly, the mixture is ground until the fineness is less than 50 mu m, 2kg of curing agent is added under the protection of nitrogen, the mixture is stirred for 30 minutes and mixed uniformly, and the low-viscosity high-toughness quick-drying finish paint containing the hyperbranched modified epoxy resin is obtained.
Example 2
A low-viscosity and high-toughness quick-drying finish paint containing hyperbranched modified epoxy resin is composed of the following raw materials: 5.5kg of hyperbranched modified epoxy resin, 3kg of diluent, 3kg of filler, 1kg of dispersant, 3kg of curing agent and 0.2kg of toughening agent;
the hyperbranched modified epoxy resin is prepared by the following steps:
dissolving 1.55kg of triethanolamine in 15L N, N-dimethylformamide, stirring and cooling for 0-5 ℃, adding 0.80kg of sodium hydride at the temperature, stirring for 15 minutes, adding 5.05kg of 4-fluorobenzaldehyde, stirring for 2 hours, adding 5L of water, stirring for 35 minutes, adding 30L of ethyl acetate, stirring for 30 minutes, standing and layering, adding 5L of water into an organic phase, washing with water, stirring for 15 minutes, standing and layering, removing a solvent by vacuum distillation of the organic phase, and recrystallizing the obtained solid with 25L of methanol to obtain a compound 1;
dissolving 2.35kg of the compound 1 obtained in the step I in 12.5L of methanol, stirring and cooling to 0-5 ℃, adding 0.65kg of sodium borohydride in three batches, stirring for half an hour after each addition, then adding the next batch, ensuring the temperature to be 0-5 ℃, stirring for 35 minutes after the last addition, heating to 20-30 ℃, stirring for 1 hour, adding 3L of water, stirring for 30 minutes, carrying out reduced pressure distillation to remove the solvent, adding 4.5L of ethyl acetate, continuously washing the organic phase with 3L of water, then adding 12.5L of petroleum ether, stirring for 7 hours until white solids are separated out, filtering, and drying the filter cake under reduced pressure to obtain a compound 2;
dissolving 2.35kg of the compound 2 obtained in the step III in 15L N, N-dimethylformamide, stirring and cooling to 0-5 ℃, adding 0.425kg of sodium hydride, stirring and reacting for 15 minutes, adding 1.875kg of epoxy chloropropane, stirring for 35 minutes, heating to 20-25 ℃, stirring and reacting for 5 hours, adding 15L of water, stirring for 35 minutes, adding 25L of ethyl acetate, stirring for 20 minutes, standing and layering, adding 15L of water into the organic phase, stirring for 10 minutes, standing and layering, removing the solvent by vacuum distillation of the organic phase, and recrystallizing the obtained solid with 20L of mixed solvent to obtain a compound 3; in the step, the water adding amount in two times is the same;
the mixed solvent is petroleum ether and ethyl acetate according to the volume ratio of 1: 1, mixing to obtain;
adding 0.35kg of the compound 3 obtained in the step three, 2.35kg of bisphenol A, 7.25kg of epoxy chloropropane and 0.40kg of tetrabutylammonium bromide into 25L of dioxane, stirring at 30 ℃ for 30 minutes, heating to 80 ℃, stirring for 1 hour, adding 7L of sodium hydroxide aqueous solution at 80 ℃ in times, stirring for reacting for 8 hours, cooling to 30 ℃, standing for layering, washing the organic phase with 30L of water, and removing the solvent by reduced pressure distillation to obtain the hyperbranched modified epoxy resin;
the mass concentration of the sodium hydroxide aqueous solution is 25 percent;
the diluent is butyl acetate;
the curing agent is triethylene tetramine;
the toughening agent is dibutyl phthalate;
the filler is quartz powder
The dispersant is BYK-P104;
the preparation method of the low-viscosity high-toughness quick-drying finish paint containing the hyperbranched modified epoxy resin comprises the following steps: 5.5kg of hyperbranched modified epoxy resin, 3kg of diluent, 3kg of filler, 1kg of dispersant and 0.2kg of toughening agent are mixed and stirred uniformly, the mixture is ground until the fineness is less than 50 mu m, 3kg of curing agent is added under the protection of nitrogen, and the mixture is stirred for 30 minutes and mixed uniformly to obtain the low-viscosity high-toughness quick-drying finish paint containing the hyperbranched modified epoxy resin.
Example 3
A low-viscosity and high-toughness quick-drying finish paint containing hyperbranched modified epoxy resin is composed of the following raw materials: 4.8kg of hyperbranched modified epoxy resin, 2.4kg of diluent, 2.8kg of filler, 0.6kg of dispersant, 2.5kg of curing agent and 0.12kg of toughening agent;
the hyperbranched modified epoxy resin is prepared by the following steps:
dissolving 1.48kg of triethanolamine in 12L N, N-dimethylformamide, stirring and cooling to 0-5 ℃, adding 0.74kg of sodium hydride at the temperature, stirring for 12 minutes, adding 4.98kg of 4-fluorobenzaldehyde, stirring for 1.5 hours, adding 4.20L of water, stirring for 35 minutes, adding 24L of ethyl acetate, stirring for 25 minutes, standing and layering, adding 4.20L of water to wash the organic phase, stirring for 12 minutes, standing and layering, removing the solvent by vacuum distillation of the organic phase, and recrystallizing the obtained solid with 18L of methanol to obtain a compound 1;
dissolving 2.34kg of the compound 1 obtained in the step I in 11L of methanol, stirring and cooling to 0-5 ℃, adding 0.62kg of sodium borohydride in three batches, stirring for 35 minutes after each addition, adding the next batch, ensuring the temperature to be 0-5 ℃, stirring for 35 minutes after the last addition, heating to 20-30 ℃, stirring for 1 hour, adding 2.7L of water, stirring for 30 minutes, carrying out reduced pressure distillation to remove the solvent, adding 4.1L of ethyl acetate, washing the organic substances with 2.7L of water successively, adding 11L of petroleum ether, stirring for 6 hours until white solids are separated out, filtering, and drying the filter cake under reduced pressure to obtain a compound 2;
dissolving 2.32kg of the compound 2 obtained in the step III in 12L N, N-dimethylformamide, stirring and cooling to 0-5 ℃, adding 0.39kg of sodium hydride, stirring and reacting for 12 minutes, adding 1.84kg of epoxy chloropropane, stirring for 35 minutes, heating to 20-25 ℃, stirring and reacting for 4.5 hours, adding 13L of water, stirring for 35 minutes, adding 22L of ethyl acetate, stirring for 20 minutes, standing and layering, adding 13L of water into the organic phase, stirring for 10 minutes, standing and layering, removing the solvent by vacuum distillation of the organic phase, and recrystallizing the obtained solid with 19L of mixed solvent to obtain a compound 3;
the mixed solvent is petroleum ether and ethyl acetate according to the volume ratio of 1: 1, mixing to obtain;
adding 0.28kg of the compound 3 obtained in the step three, 2.32kg of bisphenol A, 7.18kg of epoxy chloropropane and 0.36kg of tetrabutylammonium bromide into 22L of dioxane, stirring at 25 ℃ for 30 minutes, heating to 75 ℃, stirring for 1 hour, adding 6.80L of sodium hydroxide aqueous solution at 75 ℃ in times, stirring for reaction for 7 hours, cooling to 27 ℃, standing for layering, washing the organic phase with 24L of water, and removing the solvent by reduced pressure distillation to obtain the hyperbranched modified epoxy resin;
the mass concentration of the sodium hydroxide aqueous solution is 22 percent;
the diluent is ethyl acetate;
the curing agent is hexamethylene diamine;
the toughening agent is dimethyl phthalate;
the filler is attapulgite;
the dispersant is BYK-P105.
The preparation method of the low-viscosity high-toughness quick-drying finish paint containing the hyperbranched modified epoxy resin comprises the following steps: 4.8kg of hyperbranched modified epoxy resin, 2.4kg of diluent, 2.8kg of filler, 0.6kg of dispersant and 0.12kg of toughening agent are mixed and stirred uniformly, the mixture is ground until the fineness is less than 50 mu m, 2.5kg of curing agent is added under the protection of nitrogen, and the mixture is stirred for 30 minutes and mixed uniformly to obtain the low-viscosity high-toughness quick-drying finish paint containing the hyperbranched modified epoxy resin.
Example 4
A low-viscosity and high-toughness quick-drying finish paint containing hyperbranched modified epoxy resin is composed of the following raw materials: 5kg of hyperbranched modified epoxy resin, 2.5kg of diluent, 2.8kg of filler, 0.8kg of dispersant, 2.8kg of curing agent and 0.18kg of toughening agent;
the hyperbranched modified epoxy resin is prepared by the following steps:
dissolving 1.50kg of triethanolamine in 14L N, N-dimethylformamide, stirring and cooling to 0-5 ℃, adding 0.78kg of sodium hydride at the temperature, stirring for 14 minutes, adding 5kg of 4-fluorobenzaldehyde, stirring for 1.5 hours, adding 4.50L of water, stirring for 35 minutes, adding 25L of ethyl acetate, stirring for 25 minutes, standing and layering, adding 4.50L of water for washing an organic phase, stirring for 15 minutes, standing and layering, removing the solvent by vacuum distillation of the organic phase, and recrystallizing the obtained solid with 20L of methanol to obtain a compound 1;
dissolving 2.34kg of the compound 1 obtained in the step I in 12L of methanol, stirring and cooling to 0-5 ℃, adding 0.625kg of sodium borohydride in three batches, stirring for 35 minutes after each addition, adding the next batch, ensuring the temperature to be 0-5 ℃, stirring for 35 minutes after the last addition, heating to 25 ℃, stirring for 1 hour, adding 2.75L of water, stirring for 30 minutes, carrying out reduced pressure distillation to remove the solvent, adding 4.25kg of ethyl acetate, washing the organic substances with 2.75L of water successively, adding 12L of petroleum ether, stirring for 6 hours until white solids are separated out, filtering, and drying a filter cake under reduced pressure to obtain a compound 2;
dissolving 2.32kg of the compound 2 obtained in the step 2 in 12.5L N, N-dimethylformamide, stirring and cooling to 0-5 ℃, adding 0.40kg of sodium hydride, stirring and reacting for 20 minutes, adding 1.85kg of epoxy chloropropane, stirring for 40 minutes, heating to 24 ℃, stirring and reacting for 4.5 hours, adding 12.5L of water, stirring for 40 minutes, adding 22.5L of ethyl acetate, stirring for 20 minutes, standing and layering, adding 12.5L of water into the organic phase, stirring for 10 minutes, standing and layering, removing the solvent by vacuum distillation of the organic phase, and recrystallizing the obtained solid with 17.5L of mixed solvent to obtain a compound 3;
the mixed solvent is petroleum ether and ethyl acetate according to the volume ratio of 1: 1, mixing to obtain;
adding 0.30kg of the compound 3 obtained in the step three, 2.30kg of bisphenol A, 7.20kg of epoxy chloropropane and 0.35kg of tetrabutylammonium bromide into 24L of dioxane, stirring at 25 ℃ for 30 minutes, heating to 75 ℃, stirring for 1 hour, adding 6.80L of sodium hydroxide aqueous solution at 78 ℃ in batches, stirring for reaction for 7 hours, cooling to 25 ℃, standing for layering, washing the organic phase with 25L of water, and removing the solvent by reduced pressure distillation to obtain the hyperbranched modified epoxy resin;
the mass concentration of the sodium hydroxide aqueous solution is 24 percent;
the diluent is methyl acetate;
the curing agent is diethylenetriamine;
the toughening agent is dibutyl phthalate;
the filler is quartz powder and attapulgite according to a mass ratio of 1: 1, mixing to obtain;
the dispersant is BYK-P104.
The preparation method of the low-viscosity high-toughness quick-drying finish paint containing the hyperbranched modified epoxy resin comprises the following steps: 5kg of hyperbranched modified epoxy resin, 2.5kg of diluent, 2.8kg of filler, 0.8kg of dispersant and 0.18kg of toughening agent are mixed and stirred uniformly, the mixture is ground until the fineness is less than 50 mu m, 2.8kg of curing agent is added under the protection of nitrogen, and the mixture is stirred for 30 minutes and mixed uniformly to obtain the low-viscosity high-toughness quick-drying finish paint containing the hyperbranched modified epoxy resin.
Example 5
A low-viscosity high-toughness quick-drying finish paint containing hyperbranched modified epoxy resin comprises the components and the proportion which are completely the same as those in the embodiment 3 except that filler is treated by a silane coupling agent,
the process of treating the filler by the silane coupling agent comprises the following steps:
firing the filler at 500-600 ℃ for 1 hour, and carrying out activation pretreatment for later use;
adding a silane coupling agent into an ethanol water solution with the mass concentration of 70%, starting stirring, adding a filler into the ethanol water solution in several times, ultrasonically dispersing for 0.5 hour, then placing the filler into a drying oven, and drying the filler 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: 100: 20;
the silane coupling agent is KH 560;
the filler is attapulgite.
Example 6
A low-viscosity high-toughness quick-drying finish paint containing hyperbranched modified epoxy resin comprises the components and the proportion which are completely the same as those in the embodiment 3 except that filler is treated by a silane coupling agent,
the process of treating the filler by the silane coupling agent comprises the following steps:
firing the filler at 500-600 ℃ for at least 1 hour, and carrying out activation pretreatment for later use;
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 0.5-1 hour, then placing the filler into an oven, and drying the filler 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 0.5: 100: 30, of a nitrogen-containing gas;
the silane coupling agent is KH 570;
the filler is quartz powder and attapulgite according to a mass ratio of 1: 1 are mixed to obtain the product.
The viscosity of the low-viscosity high-toughness quick-drying finish containing the hyperbranched modified epoxy resin in the embodiments 1 to 6 is measured on an NDJ-1 type rotational viscometer at 20 ℃, the viscosity range is 1400-1600 mPa.s, the viscosity is low, and the spraying is convenient. The results of testing the paint films of the low-viscosity and high-toughness quick-drying finish paints containing the hyperbranched modified epoxy resins of examples 1 to 6 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 low-viscosity high-toughness quick-drying finish paint containing the hyperbranched modified epoxy resin has low viscosity, short surface drying time and short actual drying time, the hardness of a paint film can reach 2-3H, the hardness is high, the adhesive force is 0-1 grade, the adhesive force is strong, the flexibility is strong, and when the diameter of a shaft rod is 1mm or 2mm, the paint film does not generate reticulate patterns, cracks and peeling phenomena, and has excellent water immersion resistance, salt water resistance, acid and alkali resistance and weather resistance, so that the 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 (7)
1. A low-viscosity high-toughness quick-drying finish paint containing hyperbranched modified epoxy resin is characterized in that: the composite material comprises the following raw materials in parts by weight: 45-55 parts of hyperbranched modified epoxy resin, 20-30 parts of diluent, 20-30 parts of filler, 5-10 parts of dispersant, 20-30 parts of curing agent and 1-2 parts of toughening agent;
the hyperbranched modified epoxy resin is prepared by the following steps:
dissolving triethanolamine in N, N-dimethylformamide, stirring and cooling to 0-5 ℃, adding sodium hydride at the temperature, stirring for 10-15 minutes, adding 4-fluorobenzaldehyde, stirring for 1-2 hours, adding water, stirring for at least 30 minutes, adding ethyl acetate, stirring for 20-30 minutes, standing and layering, adding an organic phase, washing with water in an amount equal to that of the previous time, stirring for at least 10 minutes, standing and layering, removing the solvent by vacuum distillation of the organic phase, and recrystallizing the obtained solid with methanol to obtain a compound 1;
wherein the mass volume ratio of the trihydroxyethylamine to the N, N-dimethylformamide to the sodium hydride to the 4-fluorobenzaldehyde to the water to the ethyl acetate to the methanol is 145-155 g: 1-1.5L: 70-80 g: 495-505 g: 0.4-0.5L: 2-3L: 1.5-2.5L;
dissolving the compound 1 obtained in the step I in methanol, cooling to 0-5 ℃ by stirring, adding sodium borohydride in three batches, stirring for at least half an hour after each addition, adding the next batch, ensuring the temperature to be 0-5 ℃, stirring for at least half an hour after the last addition, heating to 20-30 ℃, stirring for 1 hour, adding water, stirring for 30 minutes, distilling under reduced pressure to remove the solvent, adding ethyl acetate, washing with water successively, adding petroleum ether, stirring for at least 6 hours until white solids are separated out, filtering, and drying a filter cake under reduced pressure to obtain a compound 2; in the step, the water adding amount in two times is the same;
the mass-to-volume ratio of the compound 1, methanol, sodium borohydride, water, ethyl acetate and petroleum ether obtained in the step (i) is 460-470 g: 2-2.5L: 120-130 g: 0.5-0.6L: 0.8-0.9L: 2-2.5L;
dissolving the compound 2 obtained in the step II in N, N-dimethylformamide, stirring and cooling to 0-5 ℃, adding sodium hydride, stirring and reacting for at least 10 minutes, adding epoxy chloropropane, stirring for at least 30 minutes, heating to 20-25 ℃, stirring and reacting for 4-5 hours, adding water, stirring for at least 30 minutes, adding ethyl acetate, stirring for 20 minutes, standing and layering, adding water into an organic phase, stirring for 10 minutes, standing and layering, removing the solvent by vacuum distillation of the organic phase, and recrystallizing the obtained solid with a mixed solvent to obtain a compound 3; in the step, the water adding amount in two times is the same;
the mixed solvent is petroleum ether and ethyl acetate according to the volume ratio of 1: 1, mixing to obtain;
wherein the mass-to-volume ratio of the compound 2 obtained in the second step, N-dimethylformamide, sodium hydride, epichlorohydrin, water, ethyl acetate and mixed solvent is 460-470 g: 2-3L: 75-85 g: 365-375 g: 2-3L: 4-5L: 3-4L;
adding the compound 3, the bisphenol A, the epoxy chloropropane and the tetrabutylammonium bromide obtained in the step (III) into dioxane, stirring for 30 minutes at the temperature of 20-30 ℃, heating to 70-80 ℃, stirring for 1 hour, adding a sodium hydroxide aqueous solution at the temperature of 70-80 ℃ in several times, stirring for reacting for 6-8 hours, cooling to 20-30 ℃, standing for layering, washing an organic phase with water, and distilling under reduced pressure to remove a solvent to obtain the hyperbranched modified epoxy resin;
wherein the mass volume ratio of the compound 3, bisphenol A, epoxy chloropropane, tetrabutylammonium bromide, dioxane, sodium hydroxide aqueous solution and water obtained in the step (III) is 25-35 g: 225-235 g: 715-725 g: 30-40 g: 2-2.5L: 0.65-0.7L: 2-3L;
the mass concentration of the sodium hydroxide aqueous solution is 20-25%;
the diluent is dioxane or an ester solvent;
the curing agent is an amine curing agent;
the toughening agent is phthalate;
the filler is one or two of calcium carbonate, quartz powder or attapulgite.
2. The low-viscosity high-toughness quick-drying finish paint containing the hyperbranched modified epoxy resin as claimed in claim 1, is characterized in that: the ester solvent is methyl acetate, butyl acetate or ethyl acetate.
3. The low-viscosity high-toughness quick-drying finish paint containing the hyperbranched modified epoxy resin as claimed in claim 1, is characterized in that: the amine curing agent is diethylenetriamine or hexamethylene diamine.
4. The low-viscosity high-toughness quick-drying finish paint containing the hyperbranched modified epoxy resin as claimed in claim 1, is characterized in that: the toughening agent is dimethyl phthalate or dibutyl phthalate.
5. The low-viscosity high-toughness quick-drying finish paint containing the hyperbranched modified epoxy resin as claimed in claim 1, is characterized in that: the dispersant is an epoxy dispersant CM-3191, BYK-P104 or BYK-P105 of BYK company of Germany.
6. The low-viscosity high-toughness quick-drying finish paint containing the hyperbranched modified epoxy resin as claimed in claim 1, is characterized in that: the filler is treated by a silane coupling agent, and the process is as follows:
firing the filler at 500-600 ℃ for at least 1 hour, and carrying out activation pretreatment for later use;
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 filler is one or two of calcium carbonate, quartz powder or attapulgite.
7. The preparation method of the low-viscosity high-toughness quick-drying finish paint containing the hyperbranched modified epoxy resin as claimed in claim 1 is characterized in that: the method comprises the following steps:
according to parts by weight, uniformly mixing 45-55 parts of hyperbranched modified epoxy resin, 20-30 parts of diluent, 20-30 parts of filler, 5-10 parts of dispersant and 1-2 parts of toughening agent, grinding until the fineness is less than 50 microns, adding 20-30 parts of curing agent under the protection of nitrogen, stirring for 20-30 minutes, and uniformly mixing to obtain the low-viscosity high-toughness quick-drying finish paint containing the hyperbranched modified epoxy resin;
the hyperbranched modified epoxy resin is prepared by the following steps:
dissolving triethanolamine in N, N-dimethylformamide, stirring and cooling to 0-5 ℃, adding sodium hydride at the temperature, stirring for 10-15 minutes, adding 4-fluorobenzaldehyde, stirring for 1-2 hours, adding water, stirring for at least 30 minutes, adding ethyl acetate, stirring for 20-30 minutes, standing and layering, adding an organic phase, washing with water in an amount equal to that of the previous time, stirring for at least 10 minutes, standing and layering, removing the solvent by vacuum distillation of the organic phase, and recrystallizing the obtained solid with methanol to obtain a compound 1;
wherein the mass volume ratio of the trihydroxyethylamine to the N, N-dimethylformamide to the sodium hydride to the 4-fluorobenzaldehyde to the water to the ethyl acetate to the methanol is 145-155 g: 1-1.5L: 70-80 g: 495-505 g: 0.4-0.5L: 2-3L: 1.5-2.5L;
dissolving the compound 1 obtained in the step I in methanol, cooling to 0-5 ℃ by stirring, adding sodium borohydride in three batches, stirring for at least half an hour after each addition, adding the next batch, ensuring the temperature to be 0-5 ℃, stirring for at least half an hour after the last addition, heating to 20-30 ℃, stirring for 1 hour, adding water, stirring for 30 minutes, distilling under reduced pressure to remove the solvent, adding ethyl acetate, washing with water successively, adding petroleum ether, stirring for at least 6 hours until white solids are separated out, filtering, and drying a filter cake under reduced pressure to obtain a compound 2; in the step, the water adding amount in two times is the same;
the mass-to-volume ratio of the compound 1, methanol, sodium borohydride, water, ethyl acetate and petroleum ether obtained in the step (i) is 460-470 g: 2-2.5L: 120-130 g: 0.5-0.6L: 0.8-0.9L: 2-2.5L;
dissolving the compound 2 obtained in the step II in N, N-dimethylformamide, stirring and cooling to 0-5 ℃, adding sodium hydride, stirring and reacting for at least 10 minutes, adding epoxy chloropropane, stirring for at least 30 minutes, heating to 20-25 ℃, stirring and reacting for 4-5 hours, adding water, stirring for at least 30 minutes, adding ethyl acetate, stirring for 20 minutes, standing and layering, adding water into an organic phase, stirring for 10 minutes, standing and layering, removing the solvent by vacuum distillation of the organic phase, and recrystallizing the obtained solid with a mixed solvent to obtain a compound 3; in the step, the water adding amount in two times is the same;
the mixed solvent is petroleum ether and ethyl acetate according to the volume ratio of 1: 1, mixing to obtain;
wherein the mass-to-volume ratio of the compound 2 obtained in the second step, N-dimethylformamide, sodium hydride, epichlorohydrin, water, ethyl acetate and mixed solvent is 460-470 g: 2-3L: 75-85 g: 365-375 g: 2-3L: 4-5L: 3-4L;
adding the compound 3, the bisphenol A, the epoxy chloropropane and the tetrabutylammonium bromide obtained in the step (III) into dioxane, stirring for 30 minutes at the temperature of 20-30 ℃, heating to 70-80 ℃, stirring for 1 hour, adding a sodium hydroxide aqueous solution at the temperature of 70-80 ℃ in several times, stirring for reacting for 6-8 hours, cooling to 20-30 ℃, standing for layering, washing an organic phase with water, and distilling under reduced pressure to remove a solvent to obtain the hyperbranched modified epoxy resin;
wherein the mass volume ratio of the compound 3, bisphenol A, epoxy chloropropane, tetrabutylammonium bromide, dioxane, sodium hydroxide aqueous solution and water obtained in the step (III) is 25-35 g: 225-235 g: 715-725 g: 30-40 g: 2-2.5L: 0.65-0.7L: 2-3L;
the mass concentration of the sodium hydroxide aqueous solution is 20-25%;
the diluent is dioxane or an ester solvent;
the curing agent is an amine curing agent;
the toughening agent is phthalate;
the filler is one or two of calcium carbonate, quartz powder or attapulgite.
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| 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 |
| CN117025149A (en) * | 2023-10-09 | 2023-11-10 | 烟台中品环保科技有限公司 | Aldehyde-free adhesive for non-stick steel plate and preparation method thereof |
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