Preparation method of porous high-molecular fluorescent pen point
By using a combination of porous polymer materials and surfactant, a highlighter pen tip with high water absorption and short water diversion time was prepared, which solved the problem of rough hand feeling and unstable ink output, and achieved a better writing experience.
Patent Information
- Application Number
- CN202510056558.X
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-01-14
- Publication Date
- 2025-04-18
AI Technical Summary
The existing highlighter fiber tip has a rough feel and the ink output is unstable.
Porous polymer materials are used to prepare highlighter tips. By mixing ultra-high polymer materials with surfactant in a specific proportion, sintering and cooling to form, a porous polymer highlighter tip with high water absorption and short water diversion time is prepared.
It achieves a softer feel, uniform pores, good ink adsorption effect, and excellent writing effect.
Smart Images
Figure CN119842131A_ABST
Abstract
Description
Technical Field
[0001] The invention relates to the technical field of pen making, and in particular to a method for preparing a porous polymer fluorescent pen tip. Background Art
[0002] Porous polymer materials have shown excellent performance in gas adsorption, liquid adsorption, water treatment, separation, heterogeneous catalysis, electrochemical energy storage and other fields due to their high porosity, adjustable pore structure and chemical diversity. The pen tip of the fluorescent pen adopts the characteristics of liquid adsorption. The high-performance porous material is soft in texture and is formed by semi-molten molds using only one material. At present, more than 80% of the fluorescent pens in the domestic market are fiber pens. The writing feel of fiber pens is poor. During the molding process of fiber pens, a variety of industrial glues need to be mixed and bonded, and polished into various shapes with a grinding wheel. Dust is generated during the production process, which affects the health of manufacturing workers and is not environmentally friendly, and the adhesive used does not meet food grade requirements. These pen tips feel rough and the ink output is unstable. In comparison, the porous polymer fluorescent pen tip is soft and the material is safe. Summary of the invention
[0003] The purpose of the present invention is to provide a method for preparing a porous polymer fluorescent pen tip, so as to solve the problems of rough feel and unstable ink output of existing fluorescent pen fiber tips.
[0004] In order to solve the above technical problems, the present invention specifically provides the following technical solutions: The invention discloses a porous polymer fluorescent pen tip, comprising an ultra-high molecular weight material and an auxiliary agent; the mass ratio of the auxiliary agent to the ultra-high molecular weight material is 1:100-800. Compared with a fiber pen tip, the porous polymer fluorescent pen tip is softer and has uniform pores, can effectively absorb ink, and has a good writing effect.
[0005] Preferably, the auxiliary agent is a surfactant, and the surfactant is prepared from tetrahydrofurfuryl alcohol polyoxyethylene ether, p-toluenesulfonyl chloride and 4-tert-butylphenol. Ultra-high molecular weight materials are usually hydrophobic. By using a surfactant, the hydrophilicity of the prepared porous polymer fluorescent pen tip can be significantly improved, thereby achieving a higher water absorption rate and a shorter water diversion time. It also provides a reliable basic guarantee for the further preparation of fluorescent pens with excellent writing performance.
[0006] Preferably, the ultra-high molecular weight material is at least one of ultra-high molecular weight polyethylene and ultra-high molecular weight polypropylene.
[0007] The invention discloses a method for preparing a porous polymer fluorescent pen tip, comprising: The ultra-high molecular weight material and the auxiliary agent are mixed and dried, and then added into a mold for sintering to obtain a semi-molten mixture, and finally the semi-molten mixture is cooled and formed to obtain a porous polymer fluorescent pen tip.
[0008] Preferably, the ultra-high molecular weight material is at least one of ultra-high molecular weight polyethylene and ultra-high molecular weight polypropylene.
[0009] Preferably, the mass ratio of the auxiliary agent to the ultra-high molecular weight material is 1:100-800.
[0010] Preferably, the sintering temperature is 120-220° C., and the sintering time is 15-50 min.
[0011] The invention discloses a use of a porous polymer fluorescent pen tip in preparing a fluorescent pen. The porous polymer fluorescent pen tip comprises the porous polymer fluorescent pen tip or the porous polymer fluorescent pen tip prepared by the method.
[0012] The present invention discloses a method for preparing a porous polymer fluorescent pen tip, which specifically comprises: The ultra-high molecular material is added into the mold, sintered at 120-220° C. for 15-50 minutes to obtain a semi-molten mixture, and finally the semi-molten mixture is cooled and formed to obtain a pen tip to be processed, and the pen tip to be processed is immersed in an auxiliary agent solution for 20-50 minutes, and then dried to obtain a porous polymer fluorescent pen tip.
[0013] Preferably, the additive solution is composed of a surfactant and water, and the mass ratio of the surfactant to the water is 1:80-100.
[0014] The present invention discloses a method for preparing a porous polymer fluorescent pen tip, which specifically comprises: The ultra-high molecular weight material and the auxiliary agent are mixed and dried, and then added into a mold and sintered at 120-220° C. for 15-50 minutes to obtain a semi-molten mixture, and finally the semi-molten mixture is cooled and formed to obtain a porous polymer fluorescent pen tip.
[0015] Preferably, the ultra-high molecular weight material is at least one of ultra-high molecular weight polyethylene and ultra-high molecular weight polypropylene.
[0016] Preferably, the auxiliary agent is a surfactant.
[0017] Preferably, the mass ratio of the auxiliary agent to the ultra-high molecular weight material is 1:100-800.
[0018] The present invention discloses a method for preparing a surfactant, which specifically comprises: S1: Mix tetrahydrofurfuryl alcohol polyoxyethylene ether with sodium hydroxide solution, add p-toluenesulfonyl chloride solution at 0-5°C, and then react at 20-30°C for 8-12h. After the reaction, perform rotary evaporation and extraction to separate the organic layer, dry and evaporate the organic layer, and finally recrystallize to obtain the intermediate product.
[0019] S2: Under nitrogen conditions, the intermediate product, 4-tert-butylphenol, potassium carbonate and potassium fluoroborate are added to acetonitrile, and the reaction is carried out at 65-80°C for 60-80 hours. After the reaction is completed, the filtrate is collected, and then rotary evaporation and extraction are performed to separate the organic layer, the organic layer is dried and evaporated, and finally recrystallized at 0-5°C to obtain a surfactant.
[0020] Preferably, the dosage ratio of tetrahydrofurfuryl alcohol polyoxyethylene ether to sodium hydroxide solution in S1 is 1 mol: 1.8-2.2 L.
[0021] Preferably, the sodium hydroxide solution in S1 consists of sodium hydroxide and water, and the mass ratio of the amount of sodium hydroxide to water used is 1:3-3.5.
[0022] Preferably, the p-toluenesulfonyl chloride solution in S1 is composed of p-toluenesulfonyl chloride and tetrahydrofuran, and the usage ratio of p-toluenesulfonyl chloride to tetrahydrofuran is 1 mol: 0.3-0.6 L.
[0023] Preferably, the solvent used for extraction in S1 is chloroform and water.
[0024] Preferably, the solvent used for recrystallization in S1 is diethyl ether.
[0025] Preferably, the molar ratio of the intermediate product to 4-tert-butylphenol in S2 is 1:0.8-1.3.
[0026] Preferably, the molar ratio of 4-tert-butylphenol to potassium carbonate in S2 is 1:2.6-3.5.
[0027] Preferably, the molar ratio of 4-tert-butylphenol to potassium fluoroborate in S2 is 1:1-2.
[0028] Preferably, the usage ratio of 4-tert-butylphenol to acetonitrile is 1 mol:6-7.5L.
[0029] Preferably, the solvent used for extraction in S2 is dichloromethane and water.
[0030] Preferably, the solvent used for recrystallization in S2 is diethyl ether.
[0031] More preferably, in the preparation of the porous polymer fluorescent pen tip, on the basis of using a surfactant, N-cocoyl-L-glutamate monosodium can also be used. The synergistic effect of N-cocoyl-L-glutamate monosodium and the surfactant can further optimize the performance of the porous polymer fluorescent pen tip, making it have a higher water absorption rate and a shorter water diversion time. This synergistic effect can effectively enhance the capillary action path between the porous polymer fluorescent pen tip and the ink, ensuring that the ink conducts more smoothly in the pen tip, thereby providing a more stable and smooth writing experience for the subsequent preparation of the fluorescent pen.
[0032] Preferably, the mass ratio of the surfactant to the monosodium N-cocoyl-L-glutamate used is 1:0.15-1.2.
[0033] Compared with the prior art, the present invention has the following beneficial effects: The present invention proposes a method for preparing a porous polymer fluorescent pen tip, firstly, a super polymer material and an auxiliary agent are mixed and dried, then added into a mold for sintering to obtain a semi-molten mixture, and finally the semi-molten mixture is cooled and formed to obtain a porous polymer fluorescent pen tip. The super polymer material is ultra-high molecular weight polyethylene or ultra-high molecular weight polypropylene, and the auxiliary agent is a prepared surfactant. The porous polymer fluorescent pen tip prepared by the method of the present invention not only has a high water absorption rate, but also has a short water diversion time, can quickly absorb ink, and has excellent performance. BRIEF DESCRIPTION OF THE DRAWINGS
[0034] In order to more clearly illustrate the implementation methods of the present invention or the technical solutions in the prior art, the following briefly introduces the drawings required for the implementation methods or the description of the prior art. Obviously, the drawings in the following description are only exemplary, and for ordinary technicians in this field, other implementation drawings can be derived from the provided drawings without creative work.
[0035] Figure 1 This is the SEM image of the pen tip to be treated prepared in Example 1. DETAILED DESCRIPTION
[0036] The following will be combined with the drawings in the embodiments of the present invention to clearly and completely describe the technical solutions in the embodiments of the present invention. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.
[0037] The following first describes the concepts involved in the present application in conjunction with the accompanying drawings. It should be noted that the following description of each concept is only to make the content of the present application easier to understand, and does not limit the scope of protection of the present application; at the same time, the embodiments and features in the embodiments of the present application can be combined with each other in the absence of conflict. The present application will be described in detail with reference to the accompanying drawings and in conjunction with the embodiments.
[0038] Embodiment 1: Preparation of surfactant: Tetrahydrofurfuryl alcohol polyoxyethylene ether is mixed with sodium hydroxide solution, then p-toluenesulfonyl chloride solution is added dropwise at 0°C, and then reacted at 25°C for 10 hours. After the reaction is completed, it is rotary evaporated, and then chloroform and water are added for extraction, and the organic layer is separated. The organic layer is dried and evaporated, and then ether is added for recrystallization to obtain an intermediate product. Under nitrogen conditions, the intermediate product, 4-tert-butylphenol, potassium carbonate and potassium fluoroborate are added to acetonitrile, and reacted at 70°C for 72 hours. After the reaction is completed, the filtrate is collected and rotary evaporated, and then dichloromethane and water are added for extraction, and the organic layer is separated. The organic layer is dried and evaporated, and then ether is added for recrystallization at 4°C to obtain a surfactant. The dosage ratio of tetrahydrofurfuryl alcohol polyoxyethylene ether to sodium hydroxide solution is 1 mol: 2 L, the sodium hydroxide solution is composed of sodium hydroxide and water, the mass ratio of sodium hydroxide to water is 1: 3.17, the p-toluenesulfonyl chloride solution is composed of p-toluenesulfonyl chloride and tetrahydrofuran, the dosage ratio of p-toluenesulfonyl chloride to tetrahydrofuran is 1 mol: 0.4 L. The molar ratio of the intermediate product to 4-tert-butylphenol is 1: 1, the molar ratio of 4-tert-butylphenol to potassium carbonate is 1: 3, the molar ratio of 4-tert-butylphenol to potassium fluoroborate is 1: 1.5, and the dosage ratio of 4-tert-butylphenol to acetonitrile is 1 mol: 7 L.
[0039] Preparation of porous polymer fluorescent pen tip: ultra-high molecular weight polyethylene is added to the mold, sintered at 200°C for 20 minutes to obtain a semi-molten mixture, and finally the semi-molten mixture is cooled and formed to obtain the pen tip to be treated, and the pen tip to be treated is immersed in a surfactant solution for 30 minutes, and then dried to obtain the porous polymer fluorescent pen tip. The surfactant solution is composed of a surfactant and water, and the mass ratio of the surfactant to water is 1:90. Embodiment 2: The preparation of surfactant is the same as in Example 1.
[0040] Preparation of porous polymer fluorescent pen tip: ultra-high molecular weight polyethylene and surfactant are mixed, then dried, added into a mold, sintered at 200°C for 20 minutes to obtain a semi-molten mixture, and finally the semi-molten mixture is cooled and molded to obtain a porous polymer fluorescent pen tip. The mass ratio of the surfactant to the ultra-high molecular weight polyethylene is 1:150.
[0041] Embodiment 3: The preparation of surfactant is the same as in Example 1.
[0042] Preparation of porous polymer fluorescent pen tip: The preparation of the porous polymer fluorescent pen tip in this embodiment is compared with that in Example 2, except that the mass ratio of the surfactant to the ultra-high molecular weight polyethylene used is 1:110, and other conditions and parameters are the same as in Example 2.
[0043] Embodiment 4: The preparation of surfactant is the same as in Example 1.
[0044] Preparation of porous polymer fluorescent pen tip: The preparation of the porous polymer fluorescent pen tip in this embodiment is compared with that in Example 2, except that the mass ratio of the surfactant to the ultra-high molecular weight polyethylene used is 1:200, and other conditions and parameters are the same as in Example 2.
[0045] Embodiment 5: The preparation of surfactant is the same as in Example 1.
[0046] Preparation of porous polymer fluorescent pen tip: ultra-high molecular weight polyethylene, surfactant and N-cocoyl-L-glutamate monosodium are mixed, then dried, added into a mold, sintered at 200°C for 20 minutes to obtain a semi-molten mixture, and finally the semi-molten mixture is cooled and formed to obtain a porous polymer fluorescent pen tip. The mass ratio of the surfactant to the ultra-high molecular weight polyethylene is 1:150, and the mass ratio of the surfactant to the N-cocoyl-L-glutamate monosodium is 1:0.5.
[0047] Embodiment 6: The preparation of surfactant is the same as in Example 1.
[0048] Preparation of porous polymer fluorescent pen tip: The preparation of the porous polymer fluorescent pen tip in this embodiment is compared with that in Example 5, except that the mass ratio of the surfactant to the amount of N-cocoyl-L-glutamate monosodium is 1:0.9, and the other conditions and parameters are the same as in Example 5.
[0049] Embodiment 7: The preparation of surfactant is the same as in Example 1.
[0050] Preparation of porous polymer fluorescent pen tip: The preparation of the porous polymer fluorescent pen tip in this embodiment is compared with that in Example 5, except that the mass ratio of the surfactant to the amount of N-cocoyl-L-glutamate monosodium is 1:0.3, and the other conditions and parameters are the same as in Example 5.
[0051] Comparative Example 1: The preparation of surfactant is the same as in Example 1.
[0052] Preparation of porous polymer fluorescent pen tip: The preparation of the porous polymer fluorescent pen tip in this embodiment is compared with that in Example 2, except that the mass ratio of the surfactant to the ultra-high molecular weight polyethylene used is 1:1000, and the other conditions and parameters are the same as in Example 2.
[0053] Comparative Example 2: Preparation of porous polymer fluorescent pen tip: The preparation of the porous polymer fluorescent pen tip in this embodiment is different from that in Example 5, except that no surfactant is used, and other conditions and parameters are the same as in Example 5.
[0054] Experimental Example 1: The pen tip prepared in Example 1 was subjected to SEM microstructure observation, and the results were as follows: Figure 1 As shown, the pen tip material has evenly distributed pores, which can absorb the ink in the ink bag of the fluorescent pen, so that the pen tip can release ink evenly and the color is consistent when writing.
[0055] Experimental Example 2: Determination of water absorption rate of porous polymer fluorescent pen tip: The porous polymer fluorescent pen tip prepared in Example 1-7 and Comparative Example 1-2 was dried at 80°C for 1 hour, then weighed and recorded as m1. Then, the porous polymer fluorescent pen tip was immersed in water for 1 minute, taken out and weighed again and recorded as m2. Water absorption rate = (m2-m1) / m2×100%.
[0056] Table 1 The results of water absorption test of porous polymer fluorescent pen tips
[0057] The results are shown in Table 1. The water absorption rate of the porous polymer fluorescent pen tip prepared by the preparation method of Example 1 is 39.45%, which is lower than that of Example 2. Compared with Example 3, the water absorption rate of the porous polymer fluorescent pen tip prepared by Example 3 is higher than that of Example 2, indicating that the increase of the amount of surfactant used within a certain range can effectively improve the water absorption rate of the porous polymer fluorescent pen tip; compared with Example 4, Example 2 shows that the reduction of the amount of surfactant used within a certain range will reduce the water absorption rate of the prepared porous polymer fluorescent pen tip; compared with Example 5, Example 2 shows that on the basis of using a surfactant, the use of N-cocoyl-L-glutamate monosodium can further improve the water absorption rate of the prepared porous polymer fluorescent pen tip; compared with Example 6, Example 5 shows that the water absorption rate of the prepared porous polymer fluorescent pen tip can be further improved by using N-cocoyl-L-glutamate monosodium on the basis of using a surfactant; compared with Example 6, Example 7 shows that the water absorption rate of the prepared porous polymer fluorescent pen tip can be further improved by using N-cocoyl-L-glutamate monosodium on the basis of using a surfactant. Compared with Example 7, Example 5 shows that the increase of the use amount of N-cocoyl-L-glutamate monosodium within a certain range can improve the water absorption rate of the prepared porous polymer fluorescent pen tip; Example 5 shows that the reduction of the use amount of N-cocoyl-L-glutamate monosodium within a certain range can also reduce the water absorption rate of the prepared porous polymer fluorescent pen tip; Example 2 shows that the use amount of the surfactant needs to be in a suitable range, and too low a range will cause the water absorption rate of the prepared porous polymer fluorescent pen tip to decrease; Example 5 shows that N-cocoyl-L-glutamate monosodium needs to be used together with a surfactant, and the use of N-cocoyl-L-glutamate monosodium alone has no obvious effect on improving the water absorption rate of the prepared porous polymer fluorescent pen tip.
[0058] Experimental Example 3: Determination of water diversion time of porous polymer fluorescent pen tip: The porous polymer fluorescent pen tips prepared in Examples 1-7 and Comparative Examples 1-2 are vertically immersed in an acidic blue ink solution, and the timing ends when the top of the porous polymer fluorescent pen tip under test develops color.
[0059] Table 2 Results of the water diversion time of porous polymer fluorescent pen tip
[0060] The results are shown in Table 2. The water-drawing time of the porous polymer fluorescent pen tip prepared by the preparation method of Example 1 is 24.23s, which is longer than that of Example 2. Compared with Example 3, the water-drawing time of the porous polymer fluorescent pen tip prepared by Example 3 is lower than that of Example 2, indicating that the increase in the amount of surfactant used within a certain range can effectively reduce the water-drawing time of the porous polymer fluorescent pen tip. Compared with Example 4, Example 2 shows that the reduction in the amount of surfactant used within a certain range will increase the water-drawing time of the prepared porous polymer fluorescent pen tip. Compared with Example 5, Example 2 shows that on the basis of using a surfactant, the use of N-cocoyl-L-glutamate monosodium can further reduce the water-drawing time of the porous polymer fluorescent pen tip. Compared with Example 6, The results show that the increase of the usage of N-cocoyl-L-glutamate monosodium in a certain range can reduce the water-drawing time of the prepared porous polymer fluorescent pen tip; compared with Example 7, Example 5 shows that the reduction of the usage of N-cocoyl-L-glutamate monosodium in a certain range can also increase the water-drawing time of the prepared porous polymer fluorescent pen tip; compared with Comparative Example 1, Example 2 shows that the usage of the surfactant needs to be in a suitable range, and too low a range will cause the water-drawing time of the prepared porous polymer fluorescent pen tip to increase; compared with Comparative Example 2, Example 5 shows that N-cocoyl-L-glutamate monosodium needs to be used together with a surfactant, and the use of N-cocoyl-L-glutamate monosodium alone has no obvious effect on reducing the water-drawing time of the prepared porous polymer fluorescent pen tip.
[0061] The embodiments and / or implementation methods described above are only used to illustrate the preferred embodiments and / or implementation methods for realizing the technology of the present invention, and are not intended to limit the implementation methods of the technology of the present invention in any form. Any technical personnel in this field may make slight changes or modifications to other equivalent embodiments without departing from the scope of the technical means disclosed in the content of the present invention, but they should still be regarded as technologies or embodiments that are essentially the same as the present invention.
[0062] This article uses specific examples to illustrate the principles and implementation methods of this application. The description of the above embodiments is only used to help understand the method and its core ideas of this application. The above is only the preferred implementation method of this application. It should be pointed out that due to the limitations of textual expression and the objective existence of infinite specific structures, ordinary technicians in this technical field can make several improvements, modifications or changes without departing from the principles of this application, and can also combine the above technical features in an appropriate manner; these improvements, modifications, changes or combinations, or the direct application of the concept and technical solution of the invention to other occasions without improvement, should be regarded as the scope of protection of this application.
Claims
1. A porous polymer fluorescent pen tip, comprising an ultra-high molecular weight material and an auxiliary agent; the mass ratio of the auxiliary agent to the ultra-high molecular weight material is 1:100-800.
2. The porous polymer fluorescent pen tip according to claim 1, characterized in that: The auxiliary agent is a surfactant, and the surfactant is prepared from tetrahydrofurfuryl alcohol polyoxyethylene ether, p-toluenesulfonyl chloride and 4-tert-butylphenol.
3. The porous polymer fluorescent pen tip according to claim 1, characterized in that: The ultra-high molecular weight material is at least one of ultra-high molecular weight polyethylene and ultra-high molecular weight polypropylene.
4. A method for preparing a porous polymer fluorescent pen tip, comprising: The ultra-high molecular weight material and the auxiliary agent are mixed and dried, and then added into a mold for sintering to obtain a semi-molten mixture, and finally the semi-molten mixture is cooled and formed to obtain a porous polymer fluorescent pen tip.
5. The method for preparing a porous polymer fluorescent pen tip according to claim 4, characterized in that: The ultra-high molecular weight material is at least one of ultra-high molecular weight polyethylene and ultra-high molecular weight polypropylene.
6. The method for preparing a porous polymer fluorescent pen tip according to claim 4, characterized in that: The auxiliary agent is a surfactant, and the mass ratio of the auxiliary agent to the ultra-high molecular weight material is 1:100-800.
7. The method for preparing a porous polymer fluorescent pen tip according to claim 4, characterized in that: The sintering temperature is 120-220° C., and the sintering time is 15-50 minutes.
8. Use of a porous polymer fluorescent pen tip in preparing a fluorescent pen, the porous polymer fluorescent pen tip comprising the porous polymer fluorescent pen tip according to any one of claims 1 to 3 or the porous polymer fluorescent pen tip prepared by the method according to any one of claims 4 to 7.