Modified graphene and method for preparing the same and rub-resistant ink

Abstract

The application relates to the field of modified graphene, and particularly discloses modified graphene, a preparation method thereof and a friction-resistant ink. The preparation steps comprise the following steps: modifying graphene so that the graphene has good dispersibility, high positive electricity and adhesion, can be well dispersed in the ink, and can be closely adsorbed and wound with anionic dyes and macromolecules in the ink, so that the cohesion of the ink is effectively improved, the friction-resistant performance of the ink is improved, the ink is suitable for being used in an ink containing anionic dyes, especially an ink containing sodium alginate modified carbon black, and the prepared ink can maintain stable conductive effect under external friction.

Description

TECHNICAL FIELD

[0001] The present application relates to the field of modified graphene, more particularly, it relates to a modified graphene, a preparation method thereof and a friction-resistant ink. BACKGROUND

[0002] Graphene is a two-dimensional material composed of carbon atoms, which has excellent electrical conductivity and thermal conductivity, low resistance and high tensile strength, and has a wide range of applications in the printing and electronics industries. The ink prepared using graphene has high efficient heat conduction, energy saving effect and electric spray type printing function, and also has good color expression, and has been widely used in thermoelectric nanomaterials, chips, cables, screen protectors and other fields. However, due to the high surface energy and a large number of oxide functional groups of graphene, the dispersion of graphene in the ink is not good, and the ink system cannot achieve good condensation effect, and when subjected to external force scraping, adsorption caused by van der Waals force will cause the failure of conductive ink. The wear resistance of the ink mainly reflects the cohesive force of the ink and the adhesion to the substrate. When graphene cannot be uniformly and stably compatible with the ink system, the friction resistance of the ink cannot better meet the use requirements.

[0003] In view of the above problems, how to obtain a modified graphene suitable for colored ink system is a problem to be solved at present. SUMMARY

[0004] In order to prepare a graphene suitable for preparing colored conductive ink to improve the friction resistance of the ink, the present application provides a modified graphene, a preparation method thereof and a friction-resistant ink.

[0005] In the first aspect, the present application provides a preparation method of modified graphene, comprising the following preparation steps: adding graphene and silane coupling agent into ethanol aqueous solution, ultrasonic dispersion, heating activation, filtration, adding ethanol aqueous solution and polyetherimide, ultrasonic dispersion, heating reaction, adding iodoalkane again, heating alkylation, filtration, washing, drying, to obtain modified graphene.

[0006] By adopting the technical scheme, the preparation method is simple, the prepared modified graphene can be well dispersed in the ink, and can better play the conductive role, the polyetherimide has good creep resistance, insulation and wear resistance, thereby improving the wear resistance of the ink. The surface of the modified graphene is grafted with a relatively rich cationic quaternary ammonium, the cationic concentration is relatively high, the electrostatic repulsion can improve the dispersion of the graphene, and can also adsorb the anionic dye in the ink. On the one hand, the dispersion of the dye is improved, and the coloring effect is improved. On the other hand, the macromolecular dye is further modified graphene through electrostatic assembly, the compatibility of graphene in the system is improved, the steric hindrance effect of the macromolecule improves the dispersibility of the graphene particles, and through the force of the macromolecular resin of the connecting material, the cohesion and wear resistance of the ink are improved. The surface of the modified graphene is hydrolyzed and dehydrated through the silicon-oxygen bond, polyimide modification and alkylation, thereby forming a large number of organic long chains, greatly improving the compatibility of graphene in the system, and producing a certain winding with the macromolecular segment in the ink, and the connection is more closely, the cohesion of the ink is strong, and the wear resistance is good. The modified graphene prepared by adopting the technical scheme can improve the cohesion effect through the combination of cation and anion and the winding of the chain segment in the ink containing anionic dye, thereby greatly improving the wear resistance of the ink.

[0007] Preferably, the flake diameter of the graphene is 0.5-5 μm, and the thickness is 0.8-1.2 nm; the silane coupling agent is one or more of chloropropyl trimethoxysilane and chloropropyl triethoxysilane.

[0008] By adopting the technical scheme, the modification effect of the graphene is better, the flake diameter can realize effective lapping between the graphene while being fully modified, the "bridge" effect is less, the tap density is higher, and the conductive effect is better, meeting the use requirements of the conductive ink. When the diameter-thickness ratio of the graphene is larger, the compatibility of the graphene with the ink is not good, and the graphene is easy to be detached when being rubbed. When the diameter-thickness ratio of the graphene is smaller, the lapping of the conductive path is not easy to realize, and the conductive effect is not good. When the flake diameter of the graphene is larger, the compatibility of the graphene with the ink is not good, and the prepared ink is not resistant to friction. When the flake diameter of the graphene is smaller, the dispersion effect is limitedly improved. At the same time, the quaternary ammonium segment on the modified graphene can have enough positive electricity to realize better adsorption with the anionic dye. The length of the segment is good for winding with the macromolecule in the ink system, and does not cause the organic long chain to form more coating on the graphene. The graphene flake layers can maintain good contact, the prepared ink has good conductivity, the viscosity is suitable, and the ink can realize strong infiltration and adhesion to the substrate.

[0009] Preferably, the temperature of the heating activation is 80-90℃, the time is 20-24 hours, the temperature of the heating reaction is 80-90℃, the time is 20-24 hours, and the temperature of the heating alkylation is 80-90℃, and the time is 20-24 hours.

[0010] By adopting the technical scheme, the modification effect of the graphene is further optimized, byproducts are less, the graphene after modification is fully and uniformly quaternized, and better conductive path lap joint effect can be realized while having higher positive electricity and winding segments.

[0011] In a second aspect, the application provides a modified graphene prepared by the method.

[0012] By adopting the technical scheme, the modified graphene prepared has better dispersibility in the ink, can form certain adsorption and crosslinking with anionic dyes and macromolecules in the ink, has high cohesion, and has stable conductive effect.

[0013] In a third aspect, the application provides a friction-resistant ink, which comprises the following raw materials by mass fraction:

[0014] 50-60 parts of connecting material, 3-12 parts of modified graphene, 5-15 parts of sodium alginate modified carbon black, 3-10 parts of mineral oil, and 1-5 parts of additive, wherein the connecting material comprises rosin modified phenolic resin, the additive comprises a drying agent, and the modified graphene is the modified graphene described above.

[0015] By adopting the technical scheme, the sodium alginate modified carbon black has better adhesion and also has certain negative charge, can form certain adsorption with the uniformly distributed modified graphene in the ink, and form certain adhesion with macromolecules in the system, so that the prepared ink has high cohesion, high adhesion to the substrate, stable friction resistance and stable conductive effect.

[0016] Preferably, the rosin modified phenolic resin is an epoxy grafted rosin modified phenolic resin, which comprises the following preparation steps: heating and melting rosin, introducing nitrogen protection, adding phenol and magnesium oxide, dropping formaldehyde, heating and refluxing, increasing temperature and reacting, decreasing temperature, adding epoxy chloropropane and a catalyst, reacting, vacuum distillation, stirring and dropping sodium hydroxide solution, reacting, washing, rotary evaporation, and obtaining the epoxy grafted rosin modified phenolic resin.

[0017] Any rosin modified phenolic resin obtained by any modification method can be used in the scheme of the application. By adopting the technical scheme, the preparation method is simple, byproducts are less, the yield is high, the epoxy grafted rosin modified phenolic resin prepared can realize better connection to the components of the ink system in the application, the ink system has high cohesion and good friction resistance. The epoxy grafted rosin modified phenolic resin has high hardness, wear resistance, water resistance and other excellent properties, has good compatibility with the modified graphene prepared in the application, has more active epoxy groups on the surface at the same time, improves the ink adhesion, and through a certain degree of crosslinking with the modified graphene, further improves the cohesion of the prepared ink, the prepared ink has better friction resistance and more stable conductive effect.

[0018] Preferably, the rosin modified phenolic resin is an epoxy grafted rosin modified phenolic resin, and the epoxy value is 0.20-0.24.

[0019] By adopting the above technical solution, the number of epoxy groups is appropriate, and the epoxy grafted rosin modified phenolic resin with the epoxy value is suitable for the component setting of the ink system of the present application, and the friction resistance of the ink is most significantly improved.

[0020] Preferably, the mass ratio of the modified graphene, the sodium alginate modified carbon black and the epoxy grafted rosin modified phenolic resin is (50-60):(8-11):10.

[0021] Preferably, the mass ratio of the modified graphene, the sodium alginate modified carbon black and the epoxy grafted rosin modified phenolic resin is 55:9:10.

[0022] The applicant found in production that the ink prepared under the mass ratio has the best friction resistance, which may be because the adsorption of the modified graphene and the sodium alginate modified carbon black, the crosslinking and entanglement of the modified graphene and the sodium alginate modified carbon black and the rosin modified phenolic resin are better at this time, and the ink can also achieve better wetting on the substrate, achieving a balance between the cohesion and adhesion of the ink.

[0023] Preferably, the preparation steps of the sodium alginate modified carbon black include: S1: adding carbon black into an aqueous nitric acid solution, stirring and reacting, filtering, washing, and drying to obtain oxidized carbon black; S2: adding the oxidized carbon black and an epoxy silane coupling agent into an aqueous ethanol solution, stirring uniformly, and heating to react to obtain modified carbon black; S3: dissolving sodium alginate in deionized water to obtain a sodium alginate aqueous solution, adding the modified carbon black and sodium hydroxide, and heating to react to obtain the sodium alginate modified carbon black.

[0024] The sodium alginate modified carbon black prepared by the above preparation steps has simple preparation steps, uniform distribution and no agglomeration, high adhesion and certain rheological properties, can uniformly and stably improve the cohesion of the ink, and has better friction resistance.

[0025] Preferably, the sodium alginate modified carbon black and the modified graphene are pretreated, and the pretreatment steps include: adding the sodium alginate modified carbon black and the modified graphene into an aqueous ethanol solution, ultrasonic dispersion, suction filtration, and drying to obtain pretreated carbon black-graphene.

[0026] By pretreating the sodium alginate modified carbon black and the modified graphene, the two can be uniformly and closely adsorbed and assembled, uniformly distributed in the ink to achieve stable friction resistance and conductivity.

[0027] In summary, the present application has the following beneficial effects:

[0028] The graphene is modified in the application, so that it has good dispersibility and high positive charge, and is more suitable for use in ink containing anionic dyes. By limiting the particle size of graphene, the dispersion of graphene in the ink is further improved, and the substrate can also be well infiltrated. The graphene sheet structure has good lap joint effect, and the prepared ink can stably maintain the conductive effect under friction.

[0029] The application limits the connecting material in the ink to epoxy grafted rosin modified phenolic resin, so that the modified graphene can also crosslink with the connecting material of the ink, further improving the scratch resistance of the ink. The dye is sodium alginate modified carbon black, so that the surface of the carbon black has more anions and higher adhesion. Further limiting the mass ratio of epoxy grafted rosin modified phenolic resin, modified graphene and sodium alginate modified carbon black, and the epoxy value, the prepared ink is fully adsorbed, wound and crosslinked inside, has good substrate and infiltration, strong adhesion, good friction resistance and stable conductive performance under external friction. DETAILED DESCRIPTION

[0030] To further help understand the technical solutions of the application, the following describes the technical solutions of the application in more detail by providing several specific implementation examples. All the described examples are only part of the embodiments of the application, not all;

[0031] The following specific examples and comparative examples can be combined with each other, and the same or similar concepts or processes may not be described again in some examples. The reaction devices, monomer compounds and the like involved in the following examples and comparative examples are commercially available unless otherwise specified.

[0032] Graphene with an average sheet diameter of 0.5-5pm and a thickness of 0.8nm was purchased from Pioneer Nanometer, No. XF001W; graphene with an average sheet diameter of 5-10pm and a thickness of 4-20nm was purchased from Polywin, Item No. C03041; the drying agent was Lishengyuan 701, the rosin modified phenolic resin was purchased from Kida Ink Resin 210; and the polyetherimide was purchased from Shanghai Maikelin Biochemical Technology Co., Ltd.

[0033] Preparation Example:

[0034] Epoxy grafted rosin modified phenolic resin:

[0035] Preparation Example 1:

[0036] Heat 60 g of rosin at 170 °C to melt, protect with nitrogen, add 50 g of phenol and 0.8 g of magnesium oxide, drop 50 g of formaldehyde, heat to reflux at 100 °C for 3 hours, react at 200 °C for 10 hours, cool to 100 °C, add 40 g of epoxy chloropropane, react, distill under reduced pressure, drop 15 g of 20 wt% sodium hydroxide solution, react, wash with deionized water 3 times, rotary evaporate to obtain epoxy grafted rosin modified phenolic resin.

[0037] The epoxy grafted rosin modified phenolic resin prepared in this preparation example has an epoxy value of 0.24. The same epoxy value of epoxy grafted rosin modified phenolic resin prepared by other preparation methods can also be obtained.

[0038] Preparation Example 2:

[0039] Heat 60 g of rosin at 170 °C to melt, protect with nitrogen, add 53 g of phenol and 0.8 g of magnesium oxide, drop 50 g of formaldehyde, heat to reflux at 100 °C for 3 hours, react at 210 °C for 12 hours, cool to 100 °C, add 50 g of epoxy chloropropane, react, distill under reduced pressure, drop 15 g of 20 wt% sodium hydroxide solution, react, wash with deionized water 3 times, rotary evaporate to obtain epoxy grafted rosin modified phenolic resin.

[0040] The epoxy grafted rosin modified phenolic resin prepared in this preparation example has an epoxy value of 0.27. The same epoxy value of epoxy grafted rosin modified phenolic resin prepared by other preparation methods can also be obtained.

[0041] Sodium alginate modified carbon black:

[0042] Preparation Example 3:

[0043] S1: Add 60 g of carbon black to 250 ml of 25 wt% nitric acid aqueous solution, ultrasonic dispersion for 30 minutes at 300 W, filter after reacting for 3 hours, wash with deionized water 3 times, and dry at 50 °C to obtain oxidized carbon black;

[0044] S2: Add the oxidized carbon black prepared in S1 and 5 g of epoxy silane coupling agent KH-560 to 300 ml of 70 wt% ethanol aqueous solution, stir uniformly, heat to react at 45 °C for 2 hours to obtain modified carbon black;

[0045] S3: Dissolve 3 g of sodium alginate in deionized water to obtain 300 ml of 1 wt% sodium alginate aqueous solution, add the modified carbon black prepared in S2 and 25 g of sodium hydroxide, heat to react at 100 °C for 2 hours, and filter to obtain sodium alginate modified carbon black.

[0046] Example

[0047] Modified graphene:

[0048] Example 1

[0049] Add 5 g graphene and 4 g γ-chloropropyltrimethoxysilane to 350 ml 50 vt% aqueous ethanol solution, 300 w ultrasonic dispersion for 7 minutes, 85°C heating activation for 22 hours, filtration, add 350 ml 50 vt% aqueous ethanol solution and 7 g polyetherimide, 300 w ultrasonic dispersion for 7 minutes, 85°C heating reaction for 22 hours, then add 3 g iodoethane, 40°C heating alkylation for 12 hours, filtration, deionized water washing for 3 times, 40°C drying, to obtain modified graphene.

[0050] The graphene sheet diameter of this example is 0.5-5 μm, and the thickness is 0.8 nm, which is purchased from Pioneer Nanometer, and the number is XF001W.

[0051] Example 2

[0052] Add 5 g graphene and 4 g γ-chloropropyltrimethoxysilane to 350 ml 50 vt% aqueous ethanol solution, 300 w ultrasonic dispersion for 7 minutes, 85°C heating activation for 22 hours, filtration, add 350 ml 50 vt% aqueous ethanol solution and 7 g polyetherimide, 300 w ultrasonic dispersion for 7 minutes, 85°C heating reaction for 22 hours, then add 3 g iodoethane, 40°C heating alkylation for 12 hours, filtration, deionized water washing for 3 times, 40°C drying, to obtain modified graphene.

[0053] The graphene sheet diameter of this example is 5-10 μm, and the thickness is 4-20 nm, which is purchased from Polywin, and the number is C03041.

[0054] Friction-resistant ink:

[0055] Example 3:

[0056] This example includes the following mass parts of raw materials: epoxy grafted rosin modified phenolic resin prepared in Preparation Example 1 50 g, modified graphene prepared in Example 1 10 g, sodium alginate modified carbon black prepared in Preparation Example 3 10 g, mineral oil 10 g, and drying agent 5 g.

[0057] The preparation steps are as follows: mix the components by mass, stir at a speed of 800 r / min for 30 minutes, then stir at a speed of 1000 r / min for 10 minutes, stand, and vacuum defoam to obtain the friction-resistant ink.

[0058] Example 4:

[0059] This example includes the following mass parts of raw materials: epoxy grafted rosin modified phenolic resin prepared in Preparation Example 1 50 g, modified graphene prepared in Example 1 10 g, sodium alginate modified carbon black prepared in Preparation Example 3 10 g, mineral oil 10 g, and drying agent 5 g.

[0060] The preparation steps are as follows:

[0061] S1: The sodium alginate modified carbon black and the modified graphene were added into 150 ml of 60 wt% ethanol aqueous solution, ultrasonically dispersed for 1 hour at 300 W, suction filtered, and dried at 40°C to obtain pretreated carbon black-graphene;

[0062] S2: The pretreated carbon black-graphene and the remaining components were mixed by mass, stirred at a speed of 800 r / min for 30 minutes, then stirred at a speed of 1000 r / min for 10 minutes, left to stand, and vacuum defoamed to obtain the friction-resistant ink.

[0063] Example 5:

[0064] This example includes the following raw materials by mass: the epoxy grafted rosin modified phenolic resin prepared in Preparation Example 1, 50 g; the modified graphene prepared in Example 1, 3 g; the sodium alginate modified carbon black prepared in Preparation Example 3, 15 g; mineral oil, 8 g; and drying agent, 5 g.

[0065] The preparation steps are as follows:

[0066] S1: The sodium alginate modified carbon black and the modified graphene were added into 150 ml of 60 wt% ethanol aqueous solution, ultrasonically dispersed for 1 hour at 300 W, suction filtered, and dried at 40°C to obtain pretreated carbon black-graphene;

[0067] S2: The pretreated carbon black-graphene and the remaining components were mixed by mass, stirred at a speed of 800 r / min for 30 minutes, then stirred at a speed of 1000 r / min for 10 minutes, left to stand, and vacuum defoamed to obtain the friction-resistant ink.

[0068] Example 6:

[0069] This example includes the following raw materials by mass: the epoxy grafted rosin modified phenolic resin prepared in Preparation Example 1, 55 g; the modified graphene prepared in Example 1, 12 g; the sodium alginate modified carbon black prepared in Preparation Example 3, 5 g; mineral oil, 5 g; and drying agent, 5 g.

[0070] The preparation steps are as follows:

[0071] S1: The sodium alginate modified carbon black and the modified graphene were added into 150 ml of 60 wt% ethanol aqueous solution, ultrasonically dispersed for 1 hour at 300 W, suction filtered, and dried at 40°C to obtain pretreated carbon black-graphene;

[0072] S2: The pretreated carbon black-graphene and the remaining components were mixed by mass, stirred at a speed of 800 r / min for 30 minutes, then stirred at a speed of 1000 r / min for 10 minutes, left to stand, and vacuum defoamed to obtain the friction-resistant ink.

[0073] Example 7:

[0074] This example includes the following raw materials by mass: epoxy grafted rosin modified phenol formaldehyde resin prepared in Preparation Example 1 55 g, modified graphene prepared in Example 1 7 g, sodium alginate modified carbon black prepared in Preparation Example 3 10 g, mineral oil 5 g, and drying agent 5 g.

[0075] The preparation steps are as follows:

[0076] S1: The sodium alginate modified carbon black and the modified graphene were added to 150 ml of a 60 wt% ethanol aqueous solution, ultrasonically dispersed at 300 W for 1 hour, suction filtered, and dried at 40°C to obtain pretreated carbon black-graphene;

[0077] S2: The pretreated carbon black-graphene and the remaining components were mixed by mass, stirred at a rotation speed of 800 r / min for 30 minutes, then stirred at a rotation speed of 1000 r / min for 10 minutes, allowed to stand, and vacuum defoamed to obtain the friction-resistant ink.

[0078] Example 8:

[0079] This example includes the following raw materials by mass: epoxy grafted rosin modified phenol formaldehyde resin prepared in Preparation Example 1 55 g, modified graphene prepared in Example 1 8 g, sodium alginate modified carbon black prepared in Preparation Example 3 10 g, mineral oil 5 g, and drying agent 5 g.

[0080] The preparation steps are as follows:

[0081] S1: The sodium alginate modified carbon black and the modified graphene were added to 150 ml of a 60 wt% ethanol aqueous solution, ultrasonically dispersed at 300 W for 1 hour, suction filtered, and dried at 40°C to obtain pretreated carbon black-graphene;

[0082] S2: The pretreated carbon black-graphene and the remaining components were mixed by mass, stirred at a rotation speed of 800 r / min for 30 minutes, then stirred at a rotation speed of 1000 r / min for 10 minutes, allowed to stand, and vacuum defoamed to obtain the friction-resistant ink.

[0083] Example 9:

[0084] This example includes the following raw materials by mass: epoxy grafted rosin modified phenol formaldehyde resin prepared in Preparation Example 1 55 g, modified graphene prepared in Example 1 9 g, sodium alginate modified carbon black prepared in Preparation Example 3 10 g, mineral oil 5 g, and drying agent 5 g.

[0085] The preparation steps are as follows:

[0086] S1: The sodium alginate modified carbon black and the modified graphene were added to 150 ml of a 60 wt% ethanol aqueous solution, ultrasonically dispersed at 300 W for 1 hour, suction filtered, and dried at 40°C to obtain pretreated carbon black-graphene;

[0087] S2: The pretreated carbon black-graphene and the remaining components were mixed by mass, stirred at a speed of 800 r / min for 30 minutes, then stirred at a speed of 1000 r / min for 10 minutes, left to stand, vacuum defoamed, and a friction-resistant ink was obtained.

[0088] Example 10:

[0089] This example includes the following raw materials by mass: the epoxy grafted rosin modified phenolic resin prepared in Preparation Example 1, 55 g; the modified graphene prepared in Example 1, 1 g; the sodium alginate modified carbon black prepared in Preparation Example 3, 10 g; mineral oil, 5 g; and a drying agent, 5 g.

[0090] The preparation steps are as follows:

[0091] S1: The sodium alginate modified carbon black and the modified graphene were added to 150 ml of a 60 wt% aqueous ethanol solution, ultrasonically dispersed at 300 W for 1 hour, suction filtered, and dried at 40°C to obtain pretreated carbon black-graphene;

[0092] S2: The pretreated carbon black-graphene and the remaining components were mixed by mass, stirred at a speed of 800 r / min for 30 minutes, then stirred at a speed of 1000 r / min for 10 minutes, left to stand, vacuum defoamed, and a friction-resistant ink was obtained.

[0093] Example 11:

[0094] This example includes the following raw materials by mass: the epoxy grafted rosin modified phenolic resin prepared in Preparation Example 1, 50 g; the modified graphene prepared in Example 1, 3 g; carbon black, 15 g; mineral oil, 8 g; and a drying agent, 5 g.

[0095] The preparation steps are as follows:

[0096] S1: The carbon black and the modified graphene were added to 150 ml of a 60 wt% aqueous ethanol solution, ultrasonically dispersed at 300 W for 1 hour, suction filtered, and dried at 40°C to obtain pretreated carbon black-graphene;

[0097] S2: The pretreated carbon black-graphene and the remaining components were mixed by mass, stirred at a speed of 800 r / min for 30 minutes, then stirred at a speed of 1000 r / min for 10 minutes, left to stand, vacuum defoamed, and a friction-resistant ink was obtained.

[0098] Example 12:

[0099] This example includes the following raw materials by mass: the epoxy grafted rosin modified phenolic resin prepared in Preparation Example 1, 50 g; the modified graphene prepared in Example 2, 3 g; the sodium alginate modified carbon black prepared in Preparation Example 3, 15 g; mineral oil, 8 g; and a drying agent, 5 g.

[0100] The preparation steps are as follows:

[0101] S1: The sodium alginate modified carbon black and the modified graphene were added into 150 ml of 60 wt% ethanol aqueous solution, ultrasonically dispersed at 300 W for 1 hour, suction filtered, and dried at 40°C to obtain pretreated carbon black-graphene;

[0102] S2: The pretreated carbon black-graphene and the remaining components were mixed by mass, stirred at a rotation speed of 800 r / min for 30 minutes, then stirred at a rotation speed of 1000 r / min for 10 minutes, left to stand, and vacuum defoamed to obtain the friction-resistant ink.

[0103] Example 13

[0104] This example includes the following raw materials by mass: the epoxy grafted rosin modified phenolic resin prepared in Preparation Example 2, 50 g; the modified graphene prepared in Example 1, 3 g; the sodium alginate modified carbon black prepared in Preparation Example 3, 15 g; mineral oil, 8 g; and the drying agent, 5 g.

[0105] The preparation steps are as follows:

[0106] S1: The sodium alginate modified carbon black and the modified graphene were added into 150 ml of 60 wt% ethanol aqueous solution, ultrasonically dispersed at 300 W for 1 hour, suction filtered, and dried at 40°C to obtain pretreated carbon black-graphene;

[0107] S2: The pretreated carbon black-graphene and the remaining components were mixed by mass, stirred at a rotation speed of 800 r / min for 30 minutes, then stirred at a rotation speed of 1000 r / min for 10 minutes, left to stand, and vacuum defoamed to obtain the friction-resistant ink.

[0108] Example 14

[0109] This example includes the following raw materials by mass: the rosin modified phenolic resin, 50 g; the modified graphene prepared in Example 1, 3 g; the sodium alginate modified carbon black prepared in Preparation Example 3, 15 g; mineral oil, 8 g; and the drying agent, 5 g.

[0110] The preparation steps are as follows:

[0111] S1: The sodium alginate modified carbon black and the modified graphene were added into 150 ml of 60 wt% ethanol aqueous solution, ultrasonically dispersed at 300 W for 1 hour, suction filtered, and dried at 40°C to obtain pretreated carbon black-graphene;

[0112] S2: The pretreated carbon black-graphene and the remaining components were mixed by mass, stirred at a rotation speed of 800 r / min for 30 minutes, then stirred at a rotation speed of 1000 r / min for 10 minutes, left to stand, and vacuum defoamed to obtain the friction-resistant ink.

[0113] Comparative Example

[0114] Comparative Example 1:

[0115] 5 g graphene and 4 g amino silane coupling agent KH-550 were added to 350 ml of 50 wt% aqueous ethanol solution, ultrasonically dispersed at 300 W for 7 minutes, heated at 85°C for reaction for 22 hours, filtered, washed with deionized water for 3 times, and dried at 40°C to obtain modified graphene.

[0116] The graphene sheet diameter of this comparative example was 0.5-5 μm, and the thickness was 0.8 nm, which was purchased from Pioneer Nanometer, and the number was XF001W.

[0117] Comparative Example 2:

[0118] This example included the following raw materials by mass: epoxy grafted rosin modified phenolic resin prepared in Preparation Example 1 50 g, modified graphene prepared in Comparative Example 1 3 g, sodium alginate modified carbon black prepared in Preparation Example 3 15 g, mineral oil 8 g, and drying agent 5 g.

[0119] The preparation steps were as follows:

[0120] S1: The sodium alginate modified carbon black and the modified graphene were added to 150 ml of 60 wt% aqueous ethanol solution, ultrasonically dispersed at 300 W for 1 hour, suction filtered, and dried at 40°C to obtain pretreated carbon black-graphene;

[0121] S2: The pretreated carbon black-graphene and the remaining components were mixed by mass, stirred at a rotation speed of 800 r / min for 30 minutes, and then stirred at a rotation speed of 1000 r / min for 10 minutes, and then vacuum defoamed to obtain the friction-resistant ink.

[0122] Comparative Example 3:

[0123] This example included the following raw materials by mass: epoxy grafted rosin modified phenolic resin prepared in Preparation Example 1 50 g, graphene 3 g, sodium alginate modified carbon black prepared in Preparation Example 3 15 g, mineral oil 8 g, and drying agent 5 g.

[0124] The preparation steps were as follows:

[0125] S1: The sodium alginate modified carbon black and the modified graphene were added to 150 ml of 60 wt% aqueous ethanol solution, ultrasonically dispersed at 300 W for 1 hour, suction filtered, and dried at 40°C to obtain pretreated carbon black-graphene;

[0126] S2: The pretreated carbon black-graphene and the remaining components were mixed by mass, stirred at a rotation speed of 800 r / min for 30 minutes, and then stirred at a rotation speed of 1000 r / min for 10 minutes, and then vacuum defoamed to obtain the friction-resistant ink.

[0127] The graphene sheet diameter of the present comparative example is 0.5-5 μm, and the thickness is 0.8 nm, which is purchased from Xianfeng Nano, No. XF001W.

[0128] Performance test

[0129] 1. Adhesion - Crosshatch test: Take the ink sample prepared by each example and each comparative example, respectively, and coat on PET, then cure, and then test as follows: use a knife with a width of 10 mm-12 mm, and 1 mm-1.2 mm as an interval, a total of 10 grids, draw 10x10 (100) 1 mm x 1 mm small grids on the surface of the test sample, and the crosshatch knife should cut to the bottom material when it is drawn down, and it cannot be cut only on the ink, otherwise the test is not valid; use a brush to clean the debris in the test area, then firmly stick the tested small grid with 3M-600 adhesive tape, and use a rubber eraser to rub the tape to increase the contact area and force of the tape with the tested area; hold one end of the tape with your hand, and quickly pull down the tape in the vertical direction (90°), and perform the same test twice at the same position, and determine whether it is qualified according to the degree of ink peeling, the highest standard is 5B, which means no peeling, and the lowest is 0B, which means the peeling area is greater than 65wt%.

[0130] 2. Take the ink sample prepared by each example and each comparative example, respectively, and coat a straight line on PET, then connect a battery and a light-emitting diode on both sides after curing, and then test as follows: wrap the American 0000# steel wool on a 2 cm x 2 cm square post, apply a pressure of 500 g, rub a distance of 20 mm at a speed of 50 times / min, rub back and forth on the ink line for 100 times, and observe the light-emitting diode, and record the light-emitting as yes and the non-light-emitting as no.

[0131] The results are summarized in Table 1.

[0132] Table 1

[0133] adhesion light emission adhesion light emission example 3 3B yes example 10 3B no example 4 4B yes example 11 2B yes example 5 4B yes example 12 3B yes example 6 4B yes example 13 3B yes example 7 4B yes example 14 2B yes example 8 4B yes comparative example 2 1B no example 9 5B yes comparative example 3 0B no

[0134] It can be seen from Examples 3-4 and Comparative Examples 2-3 and Table 1 that the graphene is modified in the present application, so that it has good dispersibility, high positive charge, and long organic chain segment, and is suitable for anionic dye conductive ink. The modified graphene and sodium alginate modified carbon black are pretreated, and can achieve good adsorption and winding connection effect in the ink system, and the prepared ink has good friction resistance. It can be seen from Examples 4 and 12 and Table 1 that the particle size of the graphene is limited, and the friction resistance and conductivity are better.

[0135] It can be seen from the combination of embodiments 4, 11 and table 1 that by modifying the carbon black with sodium alginate, the modified carbon black has relatively rich negative electricity and strong adhesion, and the two are closely connected after pretreatment, further improving the uniform dispersion and cohesion of the prepared ink.

[0136] It can be seen from the combination of embodiments 4-10 and table 1 that by limiting the mass ratio of the epoxy grafted rosin modified phenolic resin, the modified graphene and the sodium alginate modified carbon black, the modified graphene in the ink achieves a good balance between cohesion and adhesion to the substrate, and the prepared ink can not be damaged by external force when rubbed, which causes the conductive failure due to the large adhesion and insufficient cohesion, and the whole ink coating structure is separated from the substrate due to the large cohesion and insufficient adhesion.

[0137] It can be seen from the combination of embodiments 5, 12-14 and table 1 that by limiting the connecting material to be epoxy grafted rosin modified phenolic resin, the modified graphene can further improve the stability in the ink system by winding and crosslinking with the connecting material. By limiting the epoxy value of the epoxy grafted rosin modified phenolic resin within a certain range, the crosslinking degree is appropriate, which can not cause the ink coating to be completely debonded due to the large cohesion and insufficient adhesion, and can maintain stable conductivity after rubbing, which is suitable for use in the fields of thermoelectric nanomaterials, chips, cables, screen protectors and the like.

[0138] The specific embodiments are only an explanation of the present application, and are not a limitation of the present application. Those skilled in the art can make modifications to the embodiments without creative contribution after reading the present specification, but as long as the modifications are within the scope of the claims of the present application, they are protected by the patent law.

Claims

1. A rub-resistant ink, characterized by, The raw materials include 50-60 parts of connecting material, 3-12 parts of modified graphene, 5-15 parts of sodium alginate modified carbon black, 3-10 parts of mineral oil, and 1-5 parts of auxiliary agent; the connecting material includes epoxy grafted rosin modified phenolic resin; and the auxiliary agent includes drying agent. The modified graphene is prepared by the following steps: adding graphene and silane coupling agent into ethanol aqueous solution, ultrasonic dispersion, heating activation, filtration, adding ethanol aqueous solution and polyetherimide, ultrasonic dispersion, heating reaction, adding iodoalkane again, heating alkylation, filtration, washing, drying, and obtaining modified graphene. The graphene has a sheet diameter of 0.5-5 μm and a thickness of 0.8-1.2 nm; and the silane coupling agent is one or more of chloropropyl trimethoxysilane and chloropropyl triethoxysilane. The heating activation is performed at a temperature of 80-90 ℃ for 20-24 hours; the heating reaction is performed at a temperature of 80-90 ℃ for 20-24 hours; and the heating alkylation is performed at a temperature of 80-90 ℃ for 20-24 hours.

2. The rub-resistant ink of claim 1, wherein: The epoxy grafted rosin modified phenolic resin is prepared by the following steps: heating and melting rosin, introducing nitrogen protection, adding phenol and magnesium oxide, dropping formaldehyde, heating reflux, temperature rising reaction, temperature dropping, adding epoxy chloropropane and catalyst, reaction, vacuum distillation, stirring and dropping sodium hydroxide solution, reaction, washing, rotary evaporation, and obtaining epoxy grafted rosin modified phenolic resin.

3. The rub-resistant ink of claim 1, wherein: The epoxy grafted rosin modified phenolic resin has an epoxy value of 0.20-0.

24.

4. The rub-resistant ink of claim 1, wherein: The mass ratio of the epoxy grafted rosin modified phenolic resin, the modified graphene, and the sodium alginate modified carbon black is (50-60):(8-11):

10.

5. The rub-resistant ink of claim 1, wherein: The preparation steps of the sodium alginate modified carbon black include: S1: adding carbon black into nitric acid aqueous solution, stirring and reacting, filtration, washing, drying, and obtaining oxidized carbon black; S2: adding the oxidized carbon black and epoxy silane coupling agent into ethanol aqueous solution, stirring uniformly, heating reaction, and obtaining modified carbon black; and S3: dissolving sodium alginate in deionized water to obtain sodium alginate aqueous solution, adding modified carbon black and sodium hydroxide, heating reaction, and obtaining sodium alginate modified carbon black.

6. The rub-resistant ink of claim 1, wherein: The sodium alginate modified carbon black and the modified graphene are pretreated, and the pretreatment steps include: adding the sodium alginate modified carbon black and the modified graphene into ethanol aqueous solution, ultrasonic dispersion, suction filtration, and drying, and obtaining pretreated carbon black-graphene.