Graphene resin refill and manufacturing method thereof
By using the combination of modified graphene and thermosetting resin, the problem of uneven color of the writing traces and poor mechanical properties of the graphene resin refill is solved, and the mechanical properties of the refill and the uniformity of the writing traces is achieved. .
Patent Information
- Application Number
- CN202411358080.8
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2024-09-27
- Publication Date
- 2025-02-25
AI Technical Summary
The existing graphene resin refills have problems with uneven color of writing traces and poor mechanical properties.
Modified graphene is adopted to improve the mechanical properties of the refill core by the excellent bonding strength of modified graphene such as polyvinylpyrrolidone and carboxymethylcellulose, and the thermosetting resin and coloring agent. The deposit of porous calcium carbonate on the surface of the graphene prevents graphene agglomeration and promotes its uniform dispersion in the resin.
The mechanical properties of the refill core are improved and the uniformity of writing traces are improved, and the flexural strength and writing lubrication of the refill core are improved.
Smart Images
Figure CN119505603A_ABST
Abstract
Description
Technical Field
[0001] The present application relates to the technical field of resin pen core production, and in particular to a graphene resin pen core and a production method thereof. Background Art
[0002] Compared with the traditional graphite and clay composite lead, resin lead has the characteristics of thin core, easy processing, smooth writing and clear handwriting, and is currently the most popular lead product. For some high-end occasions, users require the lead to have both clear writing marks and high flexural strength. However, to improve the clarity of the lead's writing marks, more graphite needs to be added, and the lead with more graphite is often soft and brittle, and it is easy to break when the lead is subjected to a small force, thereby reducing the writing comfort.
[0003] Graphene is a sp 2 A two-dimensional sheet material composed of regular hexagonal honeycomb lattices composed of hybrid carbon atoms. It has a large specific surface area, and the theoretical specific surface area can reach 2630m 2 / g, and excellent mechanical properties, and also has good adsorption properties. Since graphene is very easy to accumulate, it is easy to affect the writing trace color and mechanical properties of the lead core. Summary of the invention
[0004] The present application provides a graphene resin pen core and a method for manufacturing the same, in order to solve the technical problems of the graphene resin pen core in the prior art, such as uneven color of writing traces and poor mechanical properties.
[0005] In a first aspect, the present application provides a method for manufacturing a graphene resin pen core, the method comprising: adding a thermosetting resin and a thermosetting resin into a solvent, stirring and dissolving the thermosetting resin using a high-speed stirrer to obtain a first mixed solution;
[0006] Adding a colorant, modified graphene and a plasticizer into a solvent, stirring rapidly, placing the mixture in an environment below zero degrees Celsius for 1 to 10 hours, taking the mixture out, heating it to 90 to 95 degrees Celsius, and cooling it to room temperature to obtain a second mixed solution;
[0007] The second mixed liquid is added to the first mixed liquid, and the solvent is evaporated by stirring at room temperature to 150° C., and the water is expelled by rolling with a three-roll mill, and the lead bars are extruded with an extruder.
[0008] In one possible implementation, the thermosetting resin is selected from any one of furan resin, phenolic resin, epoxy resin, β resin or polyimide; the thermoplastic resin is selected from any one of polyvinyl alcohol (PVA), low-temperature polyethylene, ethylene-vinyl acetate copolymer (EVOH) or polyoxymethylene. In one possible implementation, the solvent is selected from any one or more of tetrahydrofuran, N,N-dimethylformamide or N,N-dimethylacetamide; the mass ratio of the thermosetting resin, thermosetting resin, colorant, modified graphene and plasticizer is (0.5-0.8): (2.5-3.5): (3.8-5):
[0009] (0.33~0.68):(0.1~0.35); talcum powder is also added to the second mixed liquid, and the mass ratio of talcum powder to colorant is 0.1~0.5:1.
[0011] In one possible implementation, the colorant is selected from any one of flake graphite, artificial graphite, carbon black or boron nitride;
[0012] The plasticizer is selected from any one of dioctyl phthalate, polyethylene glycol, an emulsifier, a dispersant, and a stabilizer.
[0013] In a possible implementation manner, the modified graphene is prepared by the following method:
[0014] Adding graphene, polyvinyl pyrrolidone and carboxymethyl cellulose into water, stirring evenly, and grinding at a rotation speed of 6000 to 8000 rpm for 2 to 5 hours to obtain a graphene dispersion;
[0015] The graphene dispersion and the saturated calcium hydroxide solution are added into an emulsifier for emulsification and dispersion, centrifuged, and freeze-dried to obtain the modified graphene.
[0016] In a possible implementation manner, the mass ratio of the graphene, polyvinyl pyrrolidone and carboxymethyl cellulose is (1-2): (0.4-0.8): (0.3-0.8); the mass ratio of the graphene dispersion and the saturated calcium hydroxide solution is (1-5): (0.1-0.5); the number of layers of the graphene is less than or equal to 10 layers, and the sheet diameter of the graphene is 0.2-6 μm. In a possible implementation manner, after the lead strip is extruded using a three-roll mill, the method further includes:
[0017] Cut the lead bar into equal lengths, place the lead bar at 100-130° C. and dry it for 1-6 hours, then heat it to 150-180° C. and dry it for 8-15 hours to obtain an intermediate lead core;
[0018] The intermediate lead core is placed in an electric furnace, and the temperature is programmed to rise from room temperature to 1000-1200°C, and the temperature is kept constant for 0.5-2h. After being taken out and cooled, a lead core is obtained; wherein the programmed heating rate is 1.5-2.2°C / min. In one possible implementation, the diameter of the lead strip is 0.5-6.0mm, including but not limited to 0.3mm, 0.4mm, 0.5mm, 0.6mm, 0.7mm, 0.8mm, 0.9mm, 1.0mm, 1.1mm, 1.2mm, 1.3mm, 1.4mm, 1.5mm, 1.6mm, 1.7mm, 1.8mm, 1.9mm, 2.0mm, 3.0mm, 4.0mm, 5.0mm or 6.0mm. In a second aspect, the present application provides a graphene resin pen core, which is prepared by the method described in any one of the implementations of the first aspect.
[0019] Compared with the prior art, the graphene resin pen core and the manufacturing method thereof provided in the present application have the following beneficial effects:
[0020] 1. Modified graphene is used in this application. The graphene modified by polyvinyl pyrrolidone, carboxymethyl cellulose, etc. has excellent bonding strength with resins and colorants, which increases the bonding strength between the modified graphene and the resin, thereby improving the mechanical properties of the pen core.
[0021] 2. The modified graphene used in this application also has a lower agglomeration effect. The porous calcium carbonate deposited on the surface of the graphene can effectively prevent the graphene from agglomerating, which helps to disperse the graphene in the resin, promotes the uniformity of the dispersion of the graphene in the resin, and enables the graphene to be evenly dispersed in the pen core, thereby making the pen core have excellent writing marks. BRIEF DESCRIPTION OF THE DRAWINGS
[0022] The accompanying drawings, which are incorporated in and constitute a part of this specification, illustrate embodiments consistent with the present application and, together with the description, serve to explain the principles of the present application.
[0023] Figure 1 A process flow of a method for manufacturing a graphene resin pen core provided in an embodiment of the present application Figure 1 ;
[0024] Figure 2 A process flow of a method for manufacturing a graphene resin pen core provided in an embodiment of the present application Figure 2 .
[0025] The above drawings have shown clear embodiments of the present application, which will be described in more detail later. These drawings and text descriptions are not intended to limit the scope of the present application in any way, but to illustrate the concept of the present application to those skilled in the art by referring to specific embodiments. DETAILED DESCRIPTION
[0026] Exemplary embodiments will be described in detail herein, examples of which are shown in the accompanying drawings. When the following description refers to the drawings, the same numbers in different drawings represent the same or similar elements unless otherwise indicated. The implementations described in the following exemplary embodiments do not represent all implementations consistent with the present application. Instead, they are merely examples of devices and methods consistent with some aspects of the present application as detailed in the appended claims.
[0027] The technical solution of the present application and how the technical solution of the present application solves the above-mentioned technical problems are described in detail below with specific embodiments. The following specific embodiments can be combined with each other, and the same or similar concepts or processes may not be repeated in some embodiments. The embodiments of the present application will be described below in conjunction with the accompanying drawings.
[0028] Specifically, in the specific embodiment of the present application, the flexural strength is tested by a HY-307B flexural strength tester, and the writing lubricity and writing trace chromaticity are in accordance with the GB / T26698-2011 standard. In summary, the present application provides a graphene resin pen core and a method for making the same, the pen core writes smoothly, the pen core formula raw material cost is low, and industrial production can be achieved without changing the traditional process.
[0029] Example 1
[0030] A method for manufacturing a graphene resin pen core, comprising:
[0031] S201, adding furan resin and ethylene-vinyl acetate copolymer into tetrahydrofuran and N,N-dimethylformamide, stirring with a high-speed stirrer to dissolve them, and obtaining a first mixed solution.
[0032] S202, adding graphene, polyvinyl pyrrolidone and carboxymethyl cellulose to water, stirring evenly, and grinding at a rotation speed of 8000 rpm for 5 hours to obtain a graphene dispersion; wherein the mass ratio of graphene, polyvinyl pyrrolidone and carboxymethyl cellulose is 2:0.8:0.8.
[0033] S203, adding the graphene dispersion and the saturated calcium hydroxide solution into an emulsifier for emulsification and dispersion, centrifuging, and freeze-drying to obtain modified graphene; wherein the mass ratio of the graphene dispersion and the saturated calcium hydroxide solution is 5:0.5.
[0034] S204, adding flake graphite, modified graphene and polyethylene glycol to tetrahydrofuran and N,N-dimethylformamide, stirring rapidly, placing at -5 degrees Celsius for 10 hours, taking out, heating to 95 degrees Celsius, and cooling to room temperature to obtain a second mixed solution.
[0035] S205, adding the second mixed solution to the first mixed solution, stirring at 150° C. to evaporate the solvent,
[0036] A three-roll mill is used to roll out moisture, and an extruder is used to extrude lead bars, wherein the mass ratio of furan resin, ethylene-vinyl acetate copolymer, flake graphite, modified graphene and polyethylene glycol is 0.8:3.5:5:0.68:0.35, and the mass ratio of talcum powder and flake graphite is 0.5:1.
[0037] S206, cutting the lead bar into segments of equal length, placing them at 130° C. to dry for 6 hours, raising the temperature to 180° C., and drying them for 15 hours to obtain an intermediate lead core;
[0038] S207, placing the middle lead in an electric furnace, heating it from room temperature to 1000°C, and keeping it constant for 2 hours, taking it out and cooling it, to obtain the lead; wherein the heating rate is 2.2°C / min. After testing, the lead has a diameter of 0.69mm, a flexural strength of 266MPa, excellent writing lubricity and a writing trace chromaticity of 27.8.
[0039] Example 2
[0040] A method for manufacturing a graphene resin pen core, comprising:
[0041] S201, adding phenolic resin and ethylene-vinyl acetate copolymer into tetrahydrofuran, stirring with a high-speed stirrer to dissolve them, and obtaining a first mixed solution.
[0042] S202, adding graphene, polyvinyl pyrrolidone and carboxymethyl cellulose to water, stirring evenly, and grinding at a rotation speed of 6000 rpm for 2 hours to obtain a graphene dispersion; wherein the mass ratio of graphene, polyvinyl pyrrolidone and carboxymethyl cellulose is 1:0.4:0.3.
[0043] S203, adding the graphene dispersion and the saturated calcium hydroxide solution into an emulsifier for emulsification and dispersion, centrifuging, and freeze-drying to obtain modified graphene; wherein the mass ratio of the graphene dispersion and the saturated calcium hydroxide solution is 1:0.1.
[0044] S204, adding artificial graphite, modified graphene and dioctyl phthalate into tetrahydrofuran, stirring rapidly, placing at -10 degrees Celsius for 5 hours, taking out, heating to 90 degrees Celsius, and cooling to room temperature to obtain a second mixed solution.
[0045] S205. Add the second mixed liquid to the first mixed liquid, stir and evaporate the solvent at 120° C., use a three-roll mill to roll out water, and use an extruder to extrude the lead bars, wherein the mass ratio of phenolic resin, ethylene-vinyl acetate copolymer, artificial graphite, modified graphene and dioctyl phthalate is 0.6:3:4:0.55:0.22, and the mass ratio of talcum powder and artificial graphite is 0.3:1.
[0046] S206, cut the lead bar into equal length segments, place them at 110°C to dry for 4 hours, program the temperature to 160°C, and dry them for 12 hours to obtain an intermediate lead core; S207, place the intermediate lead core in an electric furnace, program the temperature from room temperature to 1100°C, and keep the temperature constant for 1 hour, take out and cool, and obtain the lead core; wherein the program temperature increase rate is 1.8°C / min.
[0047] After testing, the diameter of the lead core is 0.70mm, its flexural strength is 272MPa, its writing lubricity is excellent and the writing mark color is 27.9.
[0048] Example 3
[0049] A method for manufacturing a graphene resin pen core, comprising:
[0050] S201, adding furan resin and polyvinyl alcohol to tetrahydrofuran and N,N-dimethylacetamide,
[0051] The mixture was stirred and dissolved using a high-speed stirrer to obtain a first mixed solution.
[0052] S202, adding graphene, polyvinyl pyrrolidone and carboxymethyl cellulose to water, stirring evenly, and grinding at a rotation speed of 7000 rpm for 3 hours to obtain a graphene dispersion; wherein the mass ratio of graphene, polyvinyl pyrrolidone and carboxymethyl cellulose is 0.2:0.5:0.54.
[0053] S203, adding the graphene dispersion and the saturated calcium hydroxide solution into an emulsifier for emulsification and dispersion, centrifuging, and freeze-drying to obtain modified graphene; wherein the mass ratio of the graphene dispersion and the saturated calcium hydroxide solution is 2.4:0.3.
[0054] S204, adding carbon black, modified graphene and polyethylene glycol to tetrahydrofuran and N,N-dimethylacetamide, stirring rapidly, placing at -3 degrees Celsius for 6 hours, taking out, heating to 92 degrees Celsius, and cooling to room temperature to obtain a second mixed solution.
[0055] S205. Add the second mixed liquid to the first mixed liquid, stir and evaporate the solvent at 140° C., use a three-roll mill to roll out water, and use an extruder to extrude the lead bar, wherein the mass ratio of furan resin, polyvinyl alcohol, carbon black, modified graphene and polyethylene glycol is 0.7:3:4.2:0.58:0.33, and the mass ratio of talcum powder and carbon black is 0.42:1.
[0056] S206, cutting the lead bar into equal length segments, placing them at 120° C. to dry for 5 hours, raising the temperature to 170° C., and drying them for 12 hours to obtain an intermediate lead core;
[0057] S207, placing the middle lead core in an electric furnace, raising the temperature from room temperature to 1200° C., and maintaining the temperature for 1.5 hours, taking it out and cooling it to obtain the lead core; wherein the program heating rate is 2° C. / min.
[0058] After testing, the diameter of the lead core is 0.71mm, its flexural strength is 262MPa, its writing lubricity is excellent and the writing mark color is 26.7.
[0059] Comparative Example 1
[0060] The only difference between this comparative example and Example 1 is that this comparative example does not contain steps S202 and S203, and graphene is used instead of modified graphene.
[0061] After testing, the diameter of the lead core is 0.695mm, its flexural strength is 194MPa, its writing lubricity is excellent and the writing mark color is 15.6.
[0062] Comparative Example 2
[0063] The only difference between this comparative example and Example 1 is that this comparative example does not contain ethylene-vinyl acetate copolymer.
[0064] After testing, the diameter of the lead core is 0.705mm, its flexural strength is 157MPa, its writing lubricity is excellent and the writing mark color is 21.3.
[0065] Comparative Example 3
[0066] The difference between this comparative example and Example 1 is that this comparative example does not contain furan resin. After testing, the diameter of the lead is 0.71 mm, its flexural strength is 165 MPa, and the writing lubricity is
[0067] Excellent and writing trace chromaticity 20.8. Unless otherwise specified, the terms and phrases used herein have the meanings listed below. A specific term or phrase should not be considered uncertain or unclear without special definition, but should be interpreted according to the meaning generally understood by those skilled in the art. When a trade name appears in this article, it is intended to refer to its corresponding product or its active ingredient.
[0068] Unless otherwise specifically defined or reasonably judged from the context, ratios (including percentages) or parts used herein are by weight.
[0069] The terms "about" and "approximately" when used with a numerical variable generally refer to the value of that variable and all values of that variable are within experimental error (e.g., within a 95% confidence interval for the mean) or within ±10% of the specified value, or a wider range.
[0070] The expression "comprising" or its synonymous similar expressions "including", "containing" and "having" etc. are open-ended and do not exclude additional unrecited elements, steps or ingredients. The expression "consisting of excludes any element, step or ingredient not specified. The expression "consisting essentially of means that the scope is limited to the specified elements, steps or ingredients, plus the optional elements, steps or ingredients that do not materially affect the basic and novel characteristics of the claimed subject matter. It should be understood that the expression "comprising" encompasses the expressions "consisting essentially of" and "consisting of".
[0071] The term "optional" or "optionally" means that the event or situation described subsequently may or may not occur, and the description includes the occurrence of the event or situation and the non-occurrence of the event or situation. The expression "one or more" or "at least one" can represent 1, 2, 3, 4, 5, 6, 7, 8, 9 or more. The term "and / or" covers "and" and "or". The element limited by "and / or" represents any one of them and any combination thereof. For example, A and / or B covers A, B and A+B. A, B and / or C cover A, B, C, A+B, A+C, B+C and A+B+C. Those skilled in the art will easily think of other embodiments of the present application after considering the specification and practicing the invention disclosed here. The present application is intended to cover any modification, use or adaptation of the present application, which follows the general principles of the present application and includes the common knowledge or customary technical means in the art that are not disclosed in the present application. It is intended that the specification and examples be considered as exemplary only, with a true scope and spirit of the invention being indicated by the following claims.
[0072] It should be understood that the present application is not limited to the precise structures that have been described above and shown in the drawings, and that various modifications and changes may be made without departing from the scope thereof. The scope of the present application is limited only by the appended claims.
Claims
1. A method for making a graphene resin pen core, characterized in that: The preparation method comprises: adding a thermosetting resin and a thermosetting resin into a solvent, stirring the mixture with a high-speed stirrer to dissolve the mixture, and obtaining a first mixed solution; Adding a colorant, modified graphene and a plasticizer into a solvent, stirring rapidly, placing the mixture in an environment below zero degrees Celsius for 1 to 10 hours, taking the mixture out, heating it to 90 to 95 degrees Celsius, and cooling it to room temperature to obtain a second mixed solution; The second mixed liquid is added to the first mixed liquid, and the solvent is evaporated by stirring at room temperature to 150° C., and the water is expelled by rolling with a three-roll mill, and the lead bars are extruded with an extruder.
2. The method according to claim 1, characterized in that: The thermosetting resin is selected from any one of furan resin, phenolic resin, epoxy resin, β resin or polyimide; The thermoplastic resin is selected from any one of polyvinyl alcohol (PVA), low-temperature polyethylene, ethylene-vinyl acetate copolymer (EVOH) or polyoxymethylene.
3. The method according to claim 1, characterized in that: The solvent is selected from any one or more of tetrahydrofuran, N,N-dimethylformamide or N,N-dimethylacetamide; the mass ratio of the thermosetting resin, thermosetting resin, colorant, modified graphene and plasticizer is (0.5-0.8): (2.5-3.5): (3.8-5): (0.33-0.68): (0.1～0.35)； Talcum powder is also added to the second mixed liquid, and the mass ratio of the talcum powder to the colorant is 0.1-0.5:
1.
4. The method according to claim 1, characterized in that The colorant is selected from any one of flake graphite, artificial graphite, carbon black or boron nitride; The plasticizer is selected from any one of dioctyl phthalate, polyethylene glycol, an emulsifier, a dispersant, and a stabilizer.
5. The method according to claim 1, characterized in that: The modified graphene is prepared by the following method: Graphene, polyvinyl pyrrolidone and carboxymethyl cellulose are added to water, stirred evenly, and ground at a rotation speed of 6000-8000 rpm for 2-5 hours to obtain a graphene dispersion; the graphene dispersion and a saturated calcium hydroxide solution are added to an emulsifier for emulsification and dispersion, centrifuged, and freeze-dried to obtain the modified graphene.
6. The method according to claim 5, characterized in that The mass ratio of graphene, polyvinyl pyrrolidone and carboxymethyl cellulose is (1-2): (0.4-0.8): (0.3-0.8); the mass ratio of the graphene dispersion and the saturated calcium hydroxide solution is (1-5):(0.1-0.5); the number of graphene layers is less than or equal to 10 layers, and the sheet diameter of the graphene is 0.2-6 μm.
7. The method according to claim 1, characterized in that After the lead strip is extruded by the three-roller mill, the method further comprises: Cut the lead bar into equal lengths, place them at 100-130° C. and dry them for 1-6 hours, then program the temperature to 150-180° C. and dry them for 8-15 hours to obtain an intermediate pen core; The intermediate pen core is placed in an electric furnace, and the temperature is raised from room temperature to 1000-1200° C., and the temperature is kept constant for 0.5-2 hours. After being taken out and cooled, a pen core is obtained; wherein the program heating rate is 1.5-2.2° C. / min.
8. The method according to claim 1 or 7, characterized in that: The diameter of the lead strip is 0.5 to 6.0 mm, including but not limited to 0.5 mm, 0.7 mm, 0.9 mm, 1.3 mm, 2.0 mm, 3.0 mm, 4.0 mm, 5.0 mm, and 6.0 mm.
9. A graphene resin pen core, characterized in that: The pen core is manufactured by the method according to any one of claims 1 to 7.