CN113429827A

CN113429827A - Preparation method of environment-friendly nano ink

Info

Publication number: CN113429827A
Application number: CN202110690814.2A
Authority: CN
Inventors: 董凯辉
Original assignee: Individual
Current assignee: Individual
Priority date: 2021-06-22
Filing date: 2021-06-22
Publication date: 2021-09-24

Abstract

The invention discloses a preparation method of environment-friendly nano ink, which comprises the following raw materials in parts by weight: 10-15 parts of graphene, 8-10 parts of conductive nanoparticles, 15-20 parts of polyester dihydric alcohol, 15-20 parts of hexamethylene diisocyanate, 0.5-0.9 part of butyltin dilaurate, 4-6 parts of dimethylolpropionic acid, 3-5 parts of N-methylpyrrolidone, 20-25 parts of deionized water, 5-8 parts of microcrystalline wax, 2-4 parts of a stabilizer, 5-6 parts of a pigment, 3-5 parts of a modified defoaming agent and 2-4 parts of a dispersing agent. According to the invention, toxic derivatives such as benzene are not contained, the environmental pollution is less, the preparation method has the advantages of environmental protection and the like, the cost is greatly reduced by using the graphene and the conductive nanoparticles as conductive fillers to replace silver particles, and the preparation method has certain economic benefit.

Description

Preparation method of environment-friendly nano ink

Technical Field

The invention belongs to the technical field of printing materials, and relates to a preparation method of environment-friendly nano ink.

Background

Nanotechnology is a high and new technology which has profound influence in this century. Its emergence has prompted a large number of new disciplines. Such as nano-physics, nano-chemistry, nano-biology, nano-materials, etc. The research object of nano technology is substances or structures with the size of 1-100nm, including manufacturing and processing technology, characteristic and application technology, characterization and measurement technology, etc. of nano materials. Nanometer is a measure of length, however, the unit is notVery small, 1nm equal to 10^-9m, i.e., 10 parts per billion meters. It has been found that substances at the nanoscale exhibit a series of distinctive specific properties in many aspects, such as sound, light, electricity, magnetism and mechanics, due to their small size effects, surface and interface effects and quantum effects.

The difference between the composition and the manufacturing method of the nano ink and the common ink is only that the particle diameters of the added particles adopted by the two inks are very different, the particle diameters of the common ink are micron-sized, the particle diameters of the nano ink are nano-sized, the difference between the sizes of the nano ink and the nano ink is about 1000 times, and the introduction of the nano particles with specific performance brings improvement of certain links to the ink manufacturing process. The existing nano ink for printing has various problems: some printing ink contains benzene and ketone derivatives, so that the environmental pollution is large; in addition, the foaming phenomenon of the ink can be caused by adopting the aqueous polyurethane resin as a solvent, so that the environment-friendly nano ink preparation method needs to be developed to solve the problems.

Disclosure of Invention

The invention aims to provide an environment-friendly nano ink preparation method, wherein the nano ink is composed of auxiliaries such as graphene, conductive nano particles, waterborne polyurethane resin, pigment and modified defoaming agent, and has the advantages of less environmental pollution, environmental protection and the like because toxic derivatives such as benzene are not contained, the cost is greatly reduced by using the graphene and the conductive nano particles as conductive fillers to replace silver particles, and the nano ink has certain economic benefit.

The purpose of the invention can be realized by the following technical scheme:

an environment-friendly nano ink preparation method comprises the following steps:

step A1, preparing the following raw materials in parts by weight: 10-15 parts of graphene, 8-10 parts of conductive nanoparticles, 15-20 parts of polyester dihydric alcohol, 15-20 parts of hexamethylene diisocyanate, 0.5-0.9 part of butyltin dilaurate, 4-6 parts of dimethylolpropionic acid, 3-5 parts of N-methylpyrrolidone, 20-25 parts of deionized water, 5-8 parts of microcrystalline wax, 2-4 parts of a stabilizer, 5-6 parts of a pigment, 3-5 parts of a modified defoaming agent and 2-4 parts of a dispersing agent;

step A2, adding graphene into piperidine, magnetically stirring for 2-3 hours at the speed of 200-220rpm, and then performing ultrasonic dispersion for 20 minutes at the frequency of 30-50kHz to obtain a mixed solution a;

step A3, adding the conductive nanoparticles into piperidine, magnetically stirring for 3-4 hours at the speed of 220-250rpm, adding the mixed solution a prepared in the step A2, and magnetically stirring for 8-10 hours at the speed of 250-260rpm to prepare a mixed solution b;

step A4, adding polyester diol and hexamethylene diisocyanate into a three-neck flask, heating in a water bath to 85 ℃, stirring for 2-3 hours, adding butyltin dilaurate to react for 30-40 minutes, then cooling to 60 ℃, quickly adding dimethylolpropionic acid and N-methylpyrrolidone, controlling the temperature of the water bath at 60-70 ℃ to react for 10 minutes, and then continuously heating to 85 ℃ to react for 2-2.5 hours to obtain a mixed solution c;

step A5, dissolving 1, 6-hexanediol in acetone, uniformly mixing with the mixed solution b prepared in the step A3, then dropwise adding the mixed solution c prepared in the step A4, stirring and shearing at a high speed for 1-2 hours, adding triethylamine solution for emulsifying for 30-40 minutes, carrying out reduced pressure distillation, and distilling out acetone to obtain a mixed solution d;

and step A6, stirring and mixing the mixed solution d prepared in the step A5, deionized water, microcrystalline wax, a stabilizer, a pigment, a modified defoaming agent and a dispersing agent at the speed of 350rpm for 2 to 3 hours, and performing ball milling for 5 to 6 hours at the rotation speed of 400rpm to 500rpm to prepare the nano ink.

Further, the dosage of the piperidine in the step A2 is 20-30mL, and the dosage of the piperidine in the step A3 is 15-20 mL.

Further, the dosage ratio of the 1, 6-hexanediol, the acetone and the triethylamine solution in the step A5 is 20-25 g: 30-40 mL: 5-10mL of triethylamine solution, and the mass fraction of the triethylamine solution is 35-38%.

Further, in the step a6, the stabilizer is one of triethylamine or ethanolamine, the pigment is one of cochineal, alizarin red, indigo blue and realgar, and the dispersant is one or more of glycerol monostearate, ethylene bis stearamide, zinc stearate and magnesium stearate, which are mixed according to any proportion.

Further, the conductive nanoparticles are prepared by the following steps:

adding indium powder, sublimed sulfur and copper acetate monohydrate into a 23mL polytetrafluoroethylene liner, then sequentially adding 3, 5-dimethylpiperidine, distilled water and DBU into the polytetrafluoroethylene liner, stirring at room temperature for 20-30 minutes, placing in a 200 ℃ oven for reaction for 8-9 days, then taking out, naturally cooling to room temperature, washing a sample with absolute ethyl alcohol for three times, and then placing in a 50-60 ℃ vacuum oven for drying for 3-4 hours to obtain the conductive nanoparticles.

Further, the dosage ratio of the indium powder, the sublimed sulfur, the monohydrate cupric acetate, 3, 5-dimethyl piperidine, the distilled water and the DBU is 0.42-0.46 mmol: 3.45-3.89 mmol: 0.28-0.29 mmol: 3-3.5 mL: 1-2 mL: 1-1.3 mL.

Further, the modified defoaming agent is prepared by the following steps:

step S1, dissolving chloroplatinic acid in isopropanol, stirring and mixing at the speed of 200-220rpm for 6-8 hours to prepare a catalyst;

step S2, adding 1, 2-dibromo tetrafluoroethane into a flask, adding Rieke Zn, adding an ethanol solution, controlling the reaction temperature to be 65 ℃ and the reaction time to be 30-40 minutes, and preparing an intermediate 1;

the reaction process is as follows:

step S3, adding the intermediate 1 prepared in the step S2, toluene and the catalyst prepared in the step S1 into a three-neck flask, controlling the reaction temperature to be 45-50 ℃, reacting at the stirring speed of 180-;

the reaction process is as follows:

step S4, sequentially adding the intermediate 2 prepared in the step S3 and 1, 1, 3, 3-tetramethyl-1, 3-disiloxane diol into a three-neck flask, mixing and stirring at the speed of 180-;

the reaction process is as follows:

step S5, adding the intermediate 3, the fatty alcohol-polyoxyethylene ether and the toluene prepared in the step S4 into a three-neck flask, stirring and mixing at the speed of 210-220rpm for 10-20 minutes, adding a molecular sieve catalyst, controlling the reaction temperature to be 70-75 ℃, centrifuging to remove the molecular sieve catalyst after reacting for 6-7 hours, and removing the toluene under reduced pressure to obtain an intermediate 4;

the reaction process is as follows:

and step S6, adding the intermediate 4 prepared in the step S5 and silicon dioxide into a three-neck flask, heating to 80 ℃ at the stirring speed of 190-200rpm, reacting for 1-2 hours at constant temperature, adding Span80, sodium carboxymethylcellulose and deionized water, and reacting for 2-3 hours to obtain the modified defoaming agent.

Further, the dosage ratio of chloroplatinic acid to isopropanol in step S1 is 0.1-0.2 g: 80-120 mL; the dosage ratio of the 1, 2-dibromo tetrafluoroethane, Rieke Zn and the ethanol solution in the step S2 is 0.8-1 g: 0.3-0.5 mg: 15-20mL, and the mass fraction of the ethanol solution is 56%; the dosage ratio of the intermediate 1, the toluene, the catalyst, the tetramethylcyclotetrasiloxane and the activated carbon in the step S3 is 0.5-0.6 g: 2-3 g: 0.2-0.3 mg: 0.3-0.35 g: 10-12 mg.

Further, the intermediate 2, 1, 3, 3-tetramethyl-1, 3-disiloxane diol and concentrated sulfuric acid in the step S4 are used in an amount of 0.55 to 0.6 g: 0.3-0.4 g: 5-6mg of concentrated sulfuric acid, wherein the mass fraction of the concentrated sulfuric acid is 95%; the mass ratio of the intermediate 3 to the fatty alcohol-polyoxyethylene ether in the step S5 is 2:1, the dosage of toluene is 50% of the total mass of the intermediate 3 and the fatty alcohol-polyoxyethylene ether, and the dosage of the molecular sieve catalyst is 0.4% of the total mass of the intermediate 3 and the fatty alcohol-polyoxyethylene ether; the dosage ratio of the intermediate 4, the silicon dioxide, the Span80, the sodium carboxymethyl cellulose and the deionized water in the step S6 is 6-8 g: 4-6 g: 0.2-0.3 g: 0.3-0.35 g: 10-15 g.

The invention has the beneficial effects that: according to the nano ink, the nano ink is composed of the graphene, the conductive nano particles, the waterborne polyurethane resin, the pigment, the modified defoaming agent and other additives, and the nano ink is free of toxic derivatives such as benzene, has less environmental pollution and has the advantages of environmental protection and the like, the cost is greatly reduced by using the graphene and the conductive nano particles as conductive fillers to replace silver particles, and the nano ink has certain economic benefit.

Specifically, firstly, copper-based chalcogenide semiconductor nanoparticles are innovatively loaded on a graphene carrier to form a conductive filler, the band gap of the copper particles is about 3.5eV, the copper-based chalcogenide semiconductor nanoparticles have semiconductor performance, excellent conductivity is shown by combining graphene, the key is to ensure the high dispersion of the graphene and the stability of the conductive nanoparticles, the graphene nanosheets are extremely easy to agglomerate through strong van der Waals force due to the hydrophobicity of the graphene, the traditional copper nanoparticles are limited in the application of the copper-based chalcogenide semiconductor nanoparticles in the field of conductive ink due to easy agglomeration and easy oxidation of the surface, the copper-based chalcogenide semiconductor nanoparticles are prepared by a solvothermal method, the copper-based chalcogenide semiconductor nanoparticles are dissolved and dispersed by protonated organic amine piperidine to form isolated copper-rich clusters with the size of about 2-3 nanometers, the piperidine carries out charge balance on the electronegativity sites exposed on the surface of the copper-rich cluster, so that the cluster agglomeration and oxidation are effectively avoided, and in addition, the piperidine can also disperse graphene.

Because the waterborne polyurethane resin is easy to foam, the invention solves the problem by adding the modified defoaming agent, firstly 1, 2-dibromo tetrafluoroethane generates a fluorine-containing intermediate 1 with double bonds through elimination reaction, the intermediate 1 generates hydrosilylation reaction with tetramethyl cyclotetrasiloxane, fluorine is introduced into siloxane to form an intermediate 2, the intermediate 2 generates fluorine-containing polysiloxane with hydroxyl end groups through polymerization reaction with 1, 1, 3, 3-tetramethyl-1, 3-disiloxane diol, namely, the intermediate 3 generates condensation reaction with fatty alcohol polyoxyethylene ether to generate an intermediate 4, namely, the effective component of the modified defoaming agent, the polyether-organosilicon surfactant has water solubility and oil solubility, is easy to adjust, and has the low surface tension, high and low temperature resistance, ageing resistance and electrical insulation performance of organosilicon, meanwhile, the lubricating effect, the softening effect, the good spreadability and the emulsification stability provided by the polyether chain segment are achieved, in addition, the antioxidant stability and the heat resistance of the defoaming agent are remarkably improved due to the addition of the organic fluorine, and the application prospect is certain.

Detailed Description

The technical solutions of the present invention will be described clearly and completely with reference to the following embodiments, and it should be understood that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.

Example 1

step A1, preparing the following raw materials in parts by weight: 10 parts of graphene, 8 parts of conductive nanoparticles, 15 parts of polyester diol, 15 parts of hexamethylene diisocyanate, 0.5 part of butyltin dilaurate, 4 parts of dimethylolpropionic acid, 3 parts of N-methylpyrrolidone, 20 parts of deionized water, 5 parts of microcrystalline wax, 2 parts of a stabilizer, 5 parts of a pigment, 3 parts of a modified defoaming agent and 2 parts of a dispersing agent;

step A2, adding graphene into piperidine, magnetically stirring for 2 hours at the speed of 200rpm, and then placing the mixture at the frequency of 30kHz for ultrasonic dispersion for 20 minutes to prepare a mixed solution a;

step A3, adding the conductive nanoparticles into piperidine, magnetically stirring for 3 hours at the speed of 220rpm, then adding the mixed solution a prepared in the step A2, and magnetically stirring for 8 hours at the speed of 250rpm to prepare a mixed solution b;

step A4, adding polyester diol and hexamethylene diisocyanate into a three-neck flask, heating in a water bath to 85 ℃, stirring for 2 hours, adding butyltin dilaurate to react for 30 minutes, then cooling to 60 ℃, quickly adding dimethylolpropionic acid and N-methylpyrrolidone, controlling the temperature of the water bath at 60 ℃, reacting for 10 minutes, and then continuously heating to 85 ℃ to react for 2 hours to obtain a mixed solution c;

step A5, dissolving 1, 6-hexanediol in acetone, uniformly mixing with the mixed solution b prepared in the step A3, then dropwise adding the mixed solution c prepared in the step A4, stirring and shearing at a high speed for 1 hour, adding a triethylamine solution, emulsifying for 30 minutes, carrying out reduced pressure distillation, and distilling out acetone to obtain a mixed solution d;

and step A6, stirring and mixing the mixed solution d prepared in the step A5, deionized water, microcrystalline wax, a stabilizer, a pigment, a modified defoaming agent and a dispersing agent for 2 hours at the speed of 300rpm, and performing ball milling for 5 hours at the rotating speed of 400rpm of a ball mill to obtain the nano ink.

Wherein the dosage of the piperidine in the step A2 is 20mL, and the dosage of the piperidine in the step A3 is 15 mL.

Wherein the dosage ratio of the 1, 6-hexanediol, acetone and triethylamine solution in the step A5 is 20 g: 30mL of: 5mL, and the mass fraction of the triethylamine solution is 35%.

Wherein the stabilizer in the step A6 is triethylamine, the pigment is cochineal, and the dispersant is stearic acid monoglyceride.

The conductive nanoparticles are prepared by the following steps:

adding indium powder, sublimed sulfur and copper acetate monohydrate into a 23mL polytetrafluoroethylene liner, then sequentially adding 3, 5-dimethylpiperidine, distilled water and DBU into the polytetrafluoroethylene liner, stirring at room temperature for 20-30 minutes, placing in a 200 ℃ oven for reaction for 8 days, then taking out, naturally cooling to room temperature, washing a sample with absolute ethyl alcohol for three times, and placing in a 50 ℃ vacuum oven for drying for 3 hours to obtain the conductive nanoparticles.

Wherein the dosage ratio of the indium powder, the sublimed sulfur, the monohydrate cupric acetate, 3, 5-dimethyl piperidine, distilled water and DBU is 0.42 mmol: 3.45 mmol: 0.28 mmol: 3mL of: 1mL of: 1 mL.

The modified defoaming agent is prepared by the following steps:

step S1, dissolving chloroplatinic acid in isopropanol, stirring and mixing at the speed of 200rpm for 6 hours to prepare a catalyst;

step S2, adding 1, 2-dibromo tetrafluoroethane into a flask, adding Rieke Zn, adding an ethanol solution, controlling the reaction temperature to be 65 ℃ and the reaction time to be 30 minutes, and preparing an intermediate 1;

step S3, adding the intermediate 1 prepared in the step S2, toluene and the catalyst prepared in the step S1 into a three-neck flask, controlling the reaction temperature to be 45 ℃, reacting at a stirring speed of 180rpm for 1 hour, heating to 70 ℃, dropwise adding tetramethylcyclotetrasiloxane, heating to 80 ℃ after dropwise adding, reacting for 8 hours, stopping heating, cooling to room temperature, adding activated carbon, stirring at a speed of 230rpm for 5 hours, filtering, and performing rotary evaporation on the filtrate to obtain an intermediate 2;

step S4, sequentially adding the intermediate 2 prepared in the step S3 and 1, 1, 3, 3-tetramethyl-1, 3-disiloxane diol into a three-neck flask, mixing and stirring at the speed of 180rpm, dropwise adding concentrated sulfuric acid while stirring, reacting for 3 hours at 60 ℃, adding sodium bicarbonate to neutralize the concentrated sulfuric acid, and vacuumizing the obtained product at 140 ℃ to remove the unreacted intermediate 2 to obtain an intermediate 3;

step S5, adding the intermediate 3, the fatty alcohol-polyoxyethylene ether and the toluene prepared in the step S4 into a three-neck flask, stirring and mixing for 10 minutes at the speed of 210rpm, adding a molecular sieve catalyst, controlling the reaction temperature to be 70 ℃, after reacting for 6 hours, centrifuging to remove the molecular sieve catalyst, and removing the toluene under reduced pressure to obtain an intermediate 4;

and step S6, adding the intermediate 4 prepared in the step S5 and silicon dioxide into a three-neck flask, heating to 80 ℃ at a stirring speed of 190rpm, reacting for 1 hour at a constant temperature, adding Span80, sodium carboxymethylcellulose and deionized water, and reacting for 2 hours to obtain the modified defoaming agent.

Wherein the dosage ratio of chloroplatinic acid to isopropanol in step S1 is 0.1 g: 80 mL; the dosage ratio of the 1, 2-dibromo tetrafluoroethane, the Rieke Zn and the ethanol solution in the step S2 is 0.8 g: 0.3 mg: 15mL, wherein the mass fraction of the ethanol solution is 56%; the dosage ratio of the intermediate 1, the toluene, the catalyst, the tetramethylcyclotetrasiloxane and the activated carbon in the step S3 is 0.5 g: 2 g: 0.2 mg: 0.3 g: 10 mg.

Wherein the using amount ratio of the intermediate 2, 1, 3, 3-tetramethyl-1, 3-disiloxane diol and concentrated sulfuric acid in the step S4 is 0.55 g: 0.3 g: 5mg, wherein the mass fraction of concentrated sulfuric acid is 95%; the mass ratio of the intermediate 3 to the fatty alcohol-polyoxyethylene ether in the step S5 is 2:1, the dosage of toluene is 50% of the total mass of the intermediate 3 and the fatty alcohol-polyoxyethylene ether, and the dosage of the molecular sieve catalyst is 0.4% of the total mass of the intermediate 3 and the fatty alcohol-polyoxyethylene ether; the dosage ratio of the intermediate 4, the silicon dioxide, the Span80, the sodium carboxymethyl cellulose and the deionized water in the step S6 is 6 g: 4 g: 0.2 g: 0.3 g: 10 g.

Example 2

step A1, preparing the following raw materials in parts by weight: 12 parts of graphene, 9 parts of conductive nanoparticles, 17 parts of polyester diol, 17 parts of hexamethylene diisocyanate, 0.7 part of butyltin dilaurate, 5 parts of dimethylolpropionic acid, 4 parts of N-methylpyrrolidone, 23 parts of deionized water, 6 parts of microcrystalline wax, 3 parts of a stabilizer, 5 parts of a pigment, 4 parts of a modified defoaming agent and 3 parts of a dispersing agent;

step A2, adding graphene into piperidine, magnetically stirring for 2.5 hours at the speed of 210rpm, and then placing the mixture at the frequency of 40kHz for ultrasonic dispersion for 20 minutes to prepare a mixed solution a;

step A3, adding the conductive nanoparticles into piperidine, magnetically stirring for 3.5 hours at the speed of 230rpm, then adding the mixed solution a prepared in the step A2, and magnetically stirring for 9 hours at the speed of 255rpm to prepare a mixed solution b;

step A4, adding polyester diol and hexamethylene diisocyanate into a three-neck flask, heating in a water bath to 85 ℃, stirring for 2.5 hours, adding butyltin dilaurate to react for 35 minutes, then cooling to 60 ℃, quickly adding dimethylolpropionic acid and N-methylpyrrolidone, controlling the temperature of the water bath at 65 ℃ to react for 10 minutes, and then continuously heating to 85 ℃ to react for 2 hours to obtain a mixed solution c;

step A5, dissolving 1, 6-hexanediol in acetone, uniformly mixing with the mixed solution b prepared in the step A3, dropwise adding the mixed solution c prepared in the step A4, stirring and shearing at a high speed for 1 hour, adding a triethylamine solution, emulsifying for 35 minutes, carrying out reduced pressure distillation, and distilling out acetone to obtain a mixed solution d;

and step A6, stirring and mixing the mixed solution d prepared in the step A5, deionized water, microcrystalline wax, a stabilizer, a pigment, a modified defoaming agent and a dispersing agent at the speed of 320rpm for 2.5 hours, and performing ball milling for 5.5 hours at the rotating speed of 450rpm to obtain the nano ink.

Wherein the dosage of the piperidine in the step A2 is 25mL, and the dosage of the piperidine in the step A3 is 17 mL.

Wherein the dosage ratio of the 1, 6-hexanediol, acetone and triethylamine solution in the step A5 is 23 g: 35mL of: 7mL, and the mass fraction of the triethylamine solution is 36%.

Wherein the stabilizer in the step A6 is ethanolamine, the pigment is indigo, and the dispersant is stearic acid monoglyceride and ethylene bis stearamide in a mass ratio of 2:1 mixing the obtained dispersing agent.

The conductive nanoparticles are prepared by the following steps:

adding indium powder, sublimed sulfur and copper acetate monohydrate into a 23mL polytetrafluoroethylene liner, sequentially adding 3, 5-dimethylpiperidine, distilled water and DBU into the polytetrafluoroethylene liner, stirring at room temperature for 25 minutes, placing in a 200 ℃ oven for reaction for 8 days, taking out, naturally cooling to room temperature, washing a sample with absolute ethyl alcohol for three times, and placing in a 55 ℃ vacuum oven for drying for 3.5 hours to obtain the conductive nanoparticles.

Wherein the dosage ratio of the indium powder, the sublimed sulfur, the monohydrate cupric acetate, 3, 5-dimethyl piperidine, distilled water and DBU is 0.44 mmol: 3.65 mmol: 0.28 mmol: 3.3 mL: 1.5 mL: 1 mL.

The modified defoaming agent is prepared by the following steps:

step S1, dissolving chloroplatinic acid in isopropanol, stirring and mixing at the speed of 210rpm for 7 hours to prepare a catalyst;

step S2, adding 1, 2-dibromo tetrafluoroethane into a flask, adding Rieke Zn, adding an ethanol solution, controlling the reaction temperature to be 65 ℃ and the reaction time to be 35 minutes, and preparing an intermediate 1;

step S3, adding the intermediate 1 prepared in the step S2, toluene and the catalyst prepared in the step S1 into a three-neck flask, controlling the reaction temperature to be 48 ℃, reacting at the stirring speed of 190rpm for 1 hour, heating to 70 ℃, dropwise adding tetramethylcyclotetrasiloxane, heating to 80 ℃ after dropwise adding, reacting for 8 hours, stopping heating, cooling to room temperature, adding activated carbon, stirring at the speed of 240rpm for 5 hours, filtering, and performing rotary evaporation on the filtrate to obtain an intermediate 2;

step S4, sequentially adding the intermediate 2 prepared in the step S3 and 1, 1, 3, 3-tetramethyl-1, 3-disiloxane diol into a three-neck flask, mixing and stirring at the speed of 190rpm, dropwise adding concentrated sulfuric acid while stirring, reacting for 3.5 hours at 62 ℃, adding sodium bicarbonate to neutralize the concentrated sulfuric acid, and vacuumizing the obtained product at 140 ℃ to remove the unreacted intermediate 2 to obtain an intermediate 3;

step S5, adding the intermediate 3, the fatty alcohol-polyoxyethylene ether and the toluene prepared in the step S4 into a three-neck flask, stirring and mixing at the speed of 215rpm for 15 minutes, adding a molecular sieve catalyst, controlling the reaction temperature to be 70 ℃, reacting for 6 hours, centrifuging to remove the molecular sieve catalyst, and removing the toluene under reduced pressure to obtain an intermediate 4;

and step S6, adding the intermediate 4 prepared in the step S5 and silicon dioxide into a three-neck flask, heating to 80 ℃ at a stirring speed of 195rpm, reacting for 1 hour at a constant temperature, adding Span80, sodium carboxymethylcellulose and deionized water, and reacting for 2 hours to obtain the modified defoaming agent.

Wherein the dosage ratio of chloroplatinic acid to isopropanol in step S1 is 0.15 g: 100 mL; the dosage ratio of the 1, 2-dibromo tetrafluoroethane, the Rieke Zn and the ethanol solution in the step S2 is 0.9 g: 0.4 mg: 17mL, wherein the mass fraction of the ethanol solution is 56%; the dosage ratio of the intermediate 1, the toluene, the catalyst, the tetramethylcyclotetrasiloxane and the activated carbon in the step S3 is 0.55 g: 2.5 g: 0.25 mg: 0.33 g: 11 mg.

Wherein the using amount ratio of the intermediate 2, 1, 3, 3-tetramethyl-1, 3-disiloxane diol and concentrated sulfuric acid in the step S4 is 0.55 g: 0.35 g: 5.5mg, the mass fraction of concentrated sulfuric acid is 95%; the mass ratio of the intermediate 3 to the fatty alcohol-polyoxyethylene ether in the step S5 is 2:1, the dosage of toluene is 50% of the total mass of the intermediate 3 and the fatty alcohol-polyoxyethylene ether, and the dosage of the molecular sieve catalyst is 0.4% of the total mass of the intermediate 3 and the fatty alcohol-polyoxyethylene ether; the dosage ratio of the intermediate 4, the silicon dioxide, the Span80, the sodium carboxymethyl cellulose and the deionized water in the step S6 is 7 g: 5 g: 0.25 g: 0.32 g: 12 g.

Example 3

step A1, preparing the following raw materials in parts by weight: 15 parts of graphene, 10 parts of conductive nanoparticles, 20 parts of polyester diol, 20 parts of hexamethylene diisocyanate, 0.9 part of butyltin dilaurate, 6 parts of dimethylolpropionic acid, 5 parts of N-methylpyrrolidone, 25 parts of deionized water, 8 parts of microcrystalline wax, 4 parts of a stabilizer, 6 parts of a pigment, 5 parts of a modified defoaming agent and 4 parts of a dispersing agent;

step A2, adding graphene into piperidine, magnetically stirring for 3 hours at the speed of 220rpm, and then placing the mixture at the frequency of 50kHz for ultrasonic dispersion for 20 minutes to prepare a mixed solution a;

step A3, adding the conductive nanoparticles into piperidine, magnetically stirring for 4 hours at the speed of 250rpm, then adding the mixed solution a prepared in the step A2, and magnetically stirring for 10 hours at the speed of 260rpm to prepare a mixed solution b;

step A4, adding polyester diol and hexamethylene diisocyanate into a three-neck flask, heating in a water bath to 85 ℃, stirring for 3 hours, adding butyltin dilaurate to react for 40 minutes, then cooling to 60 ℃, quickly adding dimethylolpropionic acid and N-methylpyrrolidone, controlling the temperature of the water bath at 70 ℃ to react for 10 minutes, and then continuously heating to 85 ℃ to react for 2.5 hours to obtain a mixed solution c;

step A5, dissolving 1, 6-hexanediol in acetone, uniformly mixing with the mixed solution b prepared in the step A3, dropwise adding the mixed solution c prepared in the step A4, stirring and shearing at a high speed for 2 hours, adding a triethylamine solution, emulsifying for 40 minutes, carrying out reduced pressure distillation, and distilling out acetone to obtain a mixed solution d;

and step A6, stirring and mixing the mixed solution d prepared in the step A5, deionized water, microcrystalline wax, a stabilizer, a pigment, a modified defoaming agent and a dispersing agent at the speed of 350rpm for 3 hours, and performing ball milling for 6 hours at the rotating speed of 500rpm of a ball mill to obtain the nano ink.

Wherein the dosage of the piperidine in the step A2 is 30mL, and the dosage of the piperidine in the step A3 is 20 mL.

Wherein the dosage ratio of the 1, 6-hexanediol, acetone and triethylamine solution in the step A5 is 25 g: 40mL of: 10mL, and the mass fraction of the triethylamine solution is 38%.

Wherein the stabilizer in the step A6 is triethylamine, the pigment is realgar, and the dispersing agent is magnesium stearate.

The conductive nanoparticles are prepared by the following steps:

adding indium powder, sublimed sulfur and copper acetate monohydrate into a 23mL polytetrafluoroethylene liner, sequentially adding 3, 5-dimethylpiperidine, distilled water and DBU into the polytetrafluoroethylene liner, stirring at room temperature for 30 minutes, placing in a 200 ℃ oven for reaction for 9 days, taking out, naturally cooling to room temperature, washing a sample with absolute ethyl alcohol for three times, and placing in a 60 ℃ vacuum oven for drying for 4 hours to obtain the conductive nanoparticles.

Wherein the dosage ratio of the indium powder, the sublimed sulfur, the monohydrate cupric acetate, 3, 5-dimethyl piperidine, distilled water and DBU is 0.46 mmol: 3.89 mmol: 0.29 mmol: 3.5 mL: 2mL of: 1.3 mL.

The modified defoaming agent is prepared by the following steps:

step S1, dissolving chloroplatinic acid in isopropanol, stirring and mixing at the speed of 220rpm for 8 hours to prepare a catalyst;

step S2, adding 1, 2-dibromo tetrafluoroethane into a flask, adding Rieke Zn, adding an ethanol solution, controlling the reaction temperature to be 65 ℃ and the reaction time to be 40 minutes, and preparing an intermediate 1;

step S3, adding the intermediate 1 prepared in the step S2, toluene and the catalyst prepared in the step S1 into a three-neck flask, controlling the reaction temperature to be 50 ℃, reacting at the stirring speed of 200rpm for 1.5 hours, heating to 70 ℃, dropwise adding tetramethylcyclotetrasiloxane, heating to 80 ℃ after dropwise adding, reacting for 9 hours, stopping heating, cooling to room temperature, adding activated carbon, stirring at the speed of 250rpm for 6 hours, filtering, and performing rotary evaporation on the filtrate to obtain an intermediate 2;

step S4, sequentially adding the intermediate 2 prepared in the step S3 and 1, 1, 3, 3-tetramethyl-1, 3-disiloxane diol into a three-neck flask, mixing and stirring at the speed of 200rpm, dropwise adding concentrated sulfuric acid while stirring, reacting for 4 hours at 65 ℃, adding sodium bicarbonate to neutralize the concentrated sulfuric acid, and vacuumizing the obtained product at 145 ℃ to remove the unreacted intermediate 2 to obtain an intermediate 3;

step S5, adding the intermediate 3, the fatty alcohol-polyoxyethylene ether and the toluene prepared in the step S4 into a three-neck flask, stirring and mixing at the speed of 220rpm for 20 minutes, adding a molecular sieve catalyst, controlling the reaction temperature to be 75 ℃, centrifuging to remove the molecular sieve catalyst after reacting for 7 hours, and removing the toluene under reduced pressure to obtain an intermediate 4;

and step S6, adding the intermediate 4 prepared in the step S5 and silicon dioxide into a three-neck flask, heating to 80 ℃ at a stirring speed of 200rpm, reacting for 2 hours at a constant temperature, adding Span80, sodium carboxymethylcellulose and deionized water, and reacting for 3 hours to obtain the modified defoaming agent.

Wherein the dosage ratio of chloroplatinic acid to isopropanol in step S1 is 0.2 g: 120 mL; the dosage ratio of the 1, 2-dibromo tetrafluoroethane, Rieke Zn and the ethanol solution in the step S2 is 1 g: 0.5 mg: 20mL, wherein the mass fraction of the ethanol solution is 56%; the dosage ratio of the intermediate 1, the toluene, the catalyst, the tetramethylcyclotetrasiloxane and the activated carbon in the step S3 is 0.6 g: 3 g: 0.3 mg: 0.35 g: 12 mg.

Wherein the using amount ratio of the intermediate 2, 1, 3, 3-tetramethyl-1, 3-disiloxane diol and concentrated sulfuric acid in the step S4 is 0.6 g: 0.4 g: 6mg, wherein the mass fraction of concentrated sulfuric acid is 95%; the mass ratio of the intermediate 3 to the fatty alcohol-polyoxyethylene ether in the step S5 is 2:1, the dosage of toluene is 50% of the total mass of the intermediate 3 and the fatty alcohol-polyoxyethylene ether, and the dosage of the molecular sieve catalyst is 0.4% of the total mass of the intermediate 3 and the fatty alcohol-polyoxyethylene ether; the dosage ratio of the intermediate 4, the silicon dioxide, the Span80, the sodium carboxymethyl cellulose and the deionized water in the step S6 is 8 g: 6 g: 0.3 g: 0.35 g: 15 g.

Comparative example 1

Commercially available nano-inks.

Comparative example 2

Comparative example 2 preparation method of nano ink referring to example 1, except that the conductive nano particles were not added.

Carrying out performance tests on examples 1-3 and comparative examples 1 and 2, (1) carrying out volume resistivity test, adopting a four-probe method for testing, and automatically converting the resistance value of a sample by using an RTS-8 type four-probe tester; (2) the adhesion performance is measured according to the GB/T9286-1988 standard, firstly, a 2mm multiplied by 2mm grid is scribed on the ink coating to be measured, an adhesive tape is adhered on the grid and is pressed forcefully to ensure that the adhesive tape is well adhered on the ink coating, and the test data is shown in the table 1:

TABLE 1

As can be seen from the table, the nano-inks produced in examples 1 to 3 have lower volume resistivity, and have lower volume resistivity and better conductivity as the content of the graphene and the conductive nano-particles increases, and furthermore, the nano-inks produced in examples 1 to 3 have more excellent adhesion.

The preferred embodiments of the invention disclosed above are intended to be illustrative only. The preferred embodiments are not intended to be exhaustive or to limit the invention to the precise embodiments disclosed. Obviously, many modifications and variations are possible in light of the above teaching. The embodiments were chosen and described in order to best explain the principles of the invention and the practical application, to thereby enable others skilled in the art to best utilize the invention. The invention is limited only by the claims and their full scope and equivalents.

Claims

1. The preparation method of the environment-friendly nano ink is characterized by comprising the following steps of:

2. The method for preparing environment-friendly nano ink according to claim 1, characterized in that: the dosage of the piperidine in the step A2 is 20-30mL, and the dosage of the piperidine in the step A3 is 15-20 mL.

3. The method for preparing environment-friendly nano ink according to claim 1, characterized in that: the dosage ratio of the 1, 6-hexanediol, the acetone and the triethylamine solution in the step A5 is 20-25 g: 30-40 mL: 5-10mL of triethylamine solution, and the mass fraction of the triethylamine solution is 35-38%.

4. The method for preparing environment-friendly nano ink according to claim 1, characterized in that: the stabilizer in the step A6 is one of triethylamine or ethanolamine, the pigment is one of cochineal, alizarin red, indigo blue and realgar, and the dispersant is one or more of stearic acid monoglyceride, ethylene bis stearamide, zinc stearate and magnesium stearate which are mixed according to any proportion.

5. The method for preparing environment-friendly nano ink according to claim 1, characterized in that: the conductive nano-particles are prepared by the following steps:

6. The method for preparing environment-friendly nano ink according to claim 5, characterized in that: the dosage ratio of the indium powder, the sublimed sulfur, the monohydrate cupric acetate, the 3, 5-dimethyl piperidine, the distilled water and the DBU is 0.42-0.46 mmol: 3.45-3.89 mmol: 0.28-0.29 mmol: 3-3.5 mL: 1-2 mL: 1-1.3 mL.

7. The method for preparing environment-friendly nano ink according to claim 1, characterized in that: the modified defoaming agent is prepared by the following steps:

8. The method for preparing environment-friendly nano ink according to claim 7, characterized in that: the dosage ratio of the chloroplatinic acid to the isopropanol in the step S1 is 0.1-0.2 g: 80-120 mL; the dosage ratio of the 1, 2-dibromo tetrafluoroethane, Rieke Zn and the ethanol solution in the step S2 is 0.8-1 g: 0.3-0.5 mg: 15-20mL, and the mass fraction of the ethanol solution is 56%; the dosage ratio of the intermediate 1, the toluene, the catalyst, the tetramethylcyclotetrasiloxane and the activated carbon in the step S3 is 0.5-0.6 g: 2-3 g: 0.2-0.3 mg: 0.3-0.35 g: 10-12 mg.

9. The method for preparing environment-friendly nano ink according to claim 7, characterized in that: the using amount ratio of the intermediate 2, 1, 3, 3-tetramethyl-1, 3-disiloxane diol and concentrated sulfuric acid in the step S4 is 0.55-0.6 g: 0.3-0.4 g: 5-6mg of concentrated sulfuric acid, wherein the mass fraction of the concentrated sulfuric acid is 95%; the mass ratio of the intermediate 3 to the fatty alcohol-polyoxyethylene ether in the step S5 is 2:1, the dosage of toluene is 50% of the total mass of the intermediate 3 and the fatty alcohol-polyoxyethylene ether, and the dosage of the molecular sieve catalyst is 0.4% of the total mass of the intermediate 3 and the fatty alcohol-polyoxyethylene ether; the dosage ratio of the intermediate 4, the silicon dioxide, the Span80, the sodium carboxymethyl cellulose and the deionized water in the step S6 is 6-8 g: 4-6 g: 0.2-0.3 g: 0.3-0.35 g: 10-15 g.