Preparation method of environment-friendly, efficient and durable fluorescent sole material

Abstract

The present application relates to a kind of preparation methods of environment-friendly high-efficiency persistent fluorescent sole material, comprising the following steps: step 1, natural rubber, cis-butadiene rubber, styrene-butadiene rubber, thermoplastic elastomer SBS are weighed and placed in mixing machine to carry out mixing treatment, and first mixing masterbatch is obtained;Step 2, white carbon black, active fluorescent powder, lubricant, antioxidant are added to first mixing masterbatch, continue mixing treatment, and second mixing masterbatch is obtained;Step 3, second mixing masterbatch is placed in vulcanizing machine, vulcanizing agent and vulcanizing accelerator are added, and vulcanization treatment is carried out, and fluorescent sole material is obtained.The fluorescent sole material finally prepared by the present application has higher strength, elasticity and aging resistance than traditional fluorescent sole material.

Description

TECHNICAL FIELD

[0001] The present application relates to the field of shoe sole materials, in particular to a preparation method of an environmentally friendly, efficient and long-lasting fluorescent shoe sole material. BACKGROUND

[0002] Fluorescent shoe soles are made of special materials, and their principle is based on fluorescence. Fluorescence refers to the phenomenon that a substance emits light after being excited. It provides a certain visibility for the wearer and increases safety. The main component that causes the fluorescent shoe sole material to emit light is fluorescent powder. Fluorescent powder is applied in the production of shoe sole rubber materials to achieve the light-emitting effect of the shoe sole. When light shines on the fluorescent powder, the fluorescent powder will absorb the energy of the light and emit fluorescence. This fluorescence usually presents bright colors such as green, yellow or orange.

[0003] In the production process of fluorescent shoe sole materials, it is crucial to select appropriate fluorescent powder. The fluorescent powder needs to have good migration resistance and high temperature resistance to ensure that the fluorescent effect of the shoe sole remains stable in various environments. The fluorescent powder needs to be added in sufficient amount to produce a significant and long-lasting effect. However, many fluorescent powders on the market have difficulty dispersing in the rubber matrix, which can cause agglomeration, reducing the strength of the shoe sole and affecting the elasticity and aging resistance of the shoe sole. SUMMARY

[0004] In view of the problems in the prior art, the purpose of the present application is to provide a preparation method of an environmentally friendly, efficient and long-lasting fluorescent shoe sole material.

[0005] The purpose of the present application is achieved by adopting the following technical solutions:

[0006] A preparation method of an environmentally friendly, efficient and long-lasting fluorescent shoe sole material, comprising the following steps:

[0007] Step 1: Weigh natural rubber, butadiene rubber, styrene-butadiene rubber and thermoplastic elastomer SBS and place them in a mixing machine for mixing treatment to obtain a first mixing masterbatch;

[0008] Step 2: Add white carbon black, active fluorescent powder, lubricant and antioxidant to the first mixing masterbatch and continue mixing treatment to obtain a second mixing masterbatch;

[0009] Step 3: Place the second mixing masterbatch in a vulcanizing machine, add vulcanizing agent and vulcanizing accelerator, and perform vulcanization treatment to obtain a fluorescent shoe sole material.

[0010] Preferably, in step 1, the mixing treatment temperature is 128-146℃, the mixing speed is 60-80r / min, and the mixing treatment time is 12-24min.

[0011] Preferably, in the step 2, the temperature of the mixing treatment is 105-125℃, the mixing speed is 40-60r / min, and the mixing treatment time is 15-25min.

[0012] Preferably, in the step 3, the temperature of the vulcanization treatment is 155-175℃, the vulcanization pressure is 10-20MPa, and the vulcanization treatment time is 45-85min.

[0013] Preferably, the fluorescent sole material comprises, by weight fraction:

[0014] 32-54 parts of natural rubber, 18-30 parts of butadiene rubber, 35-65 parts of butadiene-styrene rubber, 11-22 parts of thermoplastic elastomer SBS, 16-32 parts of white carbon black, 8-18 parts of active fluorescent powder, 2-4 parts of lubricant, 1.5-3 parts of antioxidant, 1.3-2.6 parts of vulcanizing agent, and 2.4-4.8 parts of vulcanization accelerator.

[0015] Preferably, the natural rubber is Indonesian natural rubber SIR-10 or Indonesian natural rubber SIR-20.

[0016] Preferably, the butadiene rubber is one of BR-9000, BR-9001, and BR-9002.

[0017] Preferably, the butadiene-styrene rubber is one of SBR-1500, SBR-1502, SBR-1712, and SBR-1723.

[0018] Preferably, the thermoplastic elastomer SBS is one of SBS-T171, SBS-D1116, SBS-D1102, and SBS-D1155.

[0019] Preferably, the white carbon black is one of Degussa R-202, Degussa R-106, Degussa A-380, and Degussa A-200; more preferably, it is Degussa R-202, with a specific surface area of 100±25m 2 / g and an average particle size of 14nm.

[0020] Preferably, the lubricant is one of calcium stearate, magnesium stearate, and zinc stearate.

[0021] Preferably, the antioxidant is one of antioxidant MMBZ, antioxidant BLE, and antioxidant MB.

[0022] Preferably, the vulcanizing agent is sulfur.

[0023] Preferably, the vulcanization accelerator is one of vulcanization accelerator TMTD, vulcanization accelerator TT, vulcanization accelerator DPG, and vulcanization accelerator DM.

[0024] Preferably, the preparation method of the active fluorescent powder comprises:

[0025] S1, mixing and uniformly dispersing the fluorescent powder and anhydrous ethanol, then adding gamma-aminopropylmethyldiethoxysilane, heating to reflux, and keeping stirring for 4-8h, then centrifuging, washing and drying to obtain the aminated fluorescent powder;

[0026] S2, adding 2,3-epoxypropyl acrylate into N,N-dimethylformamide, uniformly stirring, then adding the aminated fluorescent powder, heating to 60-80℃ under the protection of nitrogen, and keeping stirring for 5-10h, then centrifuging, washing and drying to obtain the acrylated fluorescent powder;

[0027] S3, adding ethylene glycol dimercaptoacetate into N,N-dimethylformamide, uniformly stirring, then introducing nitrogen as the protective gas, adding the acrylated fluorescent powder and a photosensitizer, stirring under the irradiation of ultraviolet light for 2-5h, then centrifuging, washing and drying to obtain the active fluorescent powder.

[0028] Preferably, in S1, the color of the fluorescent powder is one of blue-green (model JCAE), sky blue (model JCBE) and yellow-green (model JCCE), the particle size is 20-40μm, and the manufacturer is Huizhou Juncai Chemical Co., Ltd.

[0029] Preferably, in S1, the mass-volume ratio of the fluorescent powder, gamma-aminopropylmethyldiethoxysilane and anhydrous ethanol is 1g:(0.18-0.36)g:(10-20)mL.

[0030] Preferably, in S2, the mass-volume ratio of the aminated fluorescent powder, 2,3-epoxypropyl acrylate and N,N-dimethylformamide is 1g:(0.39-0.78)g:(20-30)mL.

[0031] Preferably, in S3, the mass-volume ratio of the acrylated fluorescent powder, ethylene glycol dimercaptoacetate and N,N-dimethylformamide is 1g:(0.84-1.68)g:(20-30)mL.

[0032] Preferably, in S3, the photosensitizer is photosensitizer 651 or photosensitizer 659, the addition amount is 3%-7% of the mass of ethylene glycol dimercaptoacetate, and the irradiation intensity of ultraviolet light is 150-350mW / cm 2 .

[0033] The present application has the following beneficial effects:

[0034] 1. The application prepares a fluorescent sole material, which uses natural rubber, cis-butadiene rubber and styrene-butadiene rubber as main raw materials, thermoplastic elastomer SBS as a plasticizing modifier, white carbon black as a filling and reinforcing agent, active fluorescent powder as a fluorescent additive, and also adds lubricant and antioxidant as additives, so that the prepared fluorescent sole material has higher strength, elasticity and aging resistance than traditional fluorescent sole materials.

[0035] 2. In order to improve the influence of fluorescent powder on rubber material, the surface of the fluorescent powder is modified. The specific process is that the surface of the fluorescent powder is first activated with amino, then the epoxy group in the acrylic-2,3-epoxy propyl ester is combined to obtain the fluorescent powder grafted with acrylic acid, and then the click chemistry reaction with dimercaptoacetic acid ethylene glycol ester containing mercapto is carried out, so that the activated fluorescent powder coated with organic matter is obtained.

[0036] 3. In the preparation process of the activated fluorescent powder, the acrylic-2,3-epoxy propyl ester used is a compound containing epoxy and olefin groups, which is commonly used in adhesives. The application utilizes the epoxy group in the structure to combine with the amino group in the amino-activated fluorescent powder and graft on the surface of the fluorescent powder. The dimercaptoacetic acid ethylene glycol ester is a compound containing double mercapto groups, which is commonly used in chemical industry as a polymerization modifier or a stabilizer for polymers. The mercapto group is crosslinked and combined with the double bond in the acrylic-activated fluorescent powder to generate a sulfide group coated on the surface of the fluorescent powder, which enhances the surface activity of the fluorescent powder and also enhances the performance of the rubber material. BRIEF DESCRIPTION OF DRAWINGS

[0037] The application is further described by using the drawings, but the embodiments in the drawings do not constitute any limitation on the application. For ordinary skilled persons in the art, other drawings can be obtained without creative labor on the basis of the following drawings.

[0038] Figure 1 is a micrograph of the environmentally friendly, high-efficiency and long-lasting fluorescent sole material prepared in Example 1 of the application;

[0039] Figure 2 is a product diagram of the environmentally friendly, high-efficiency and long-lasting fluorescent sole prepared in Example 1 of the application. DETAILED DESCRIPTION

[0040] The technical solutions of the present application are described below through specific examples. It should be understood that the one or more method steps mentioned in the present application do not exclude other method steps before and after the combination steps or other method steps inserted between the explicitly mentioned steps; it should also be understood that the examples are only used to illustrate the present application and not to limit the scope of the present application. Moreover, unless otherwise specified, the numbering of the method steps is only a convenient tool to identify the method steps and is not a limitation on the arrangement order of the method steps or the scope of the implementation of the present application, and the change or adjustment of the relative relationship without substantial change of the technical content is also considered as the scope of the implementation of the present application.

[0041] In order to better understand the above technical solutions, the exemplary embodiments of the present application are described in more detail below. Although exemplary embodiments of the present application are shown, it should be understood that the present application can be implemented in various forms and should not be limited by the embodiments described herein. On the contrary, these embodiments are provided to enable a more thorough understanding of the present application and to fully convey the scope of the present application to those skilled in the art.

[0042] The color of the fluorescent powder used in the examples is one of blue-green (model number JCAE), sky blue (model number JCBE), and yellow-green (model number JCCE), and the particle size is 20-40 μm, and the manufacturer is Huizhou Juncai Chemical Co., Ltd.

[0043] The present application is further described below in combination with the following examples.

[0044] Example 1

[0045] A preparation method of an environmentally friendly, efficient, and long-lasting fluorescent sole material, comprising the following steps:

[0046] Step 1, weigh natural rubber, butadiene rubber, styrene-butadiene rubber, and thermoplastic elastomer SBS and place them in a mixer, and perform mixing treatment at 135℃ for 16 min at a mixing speed of 70 r / min to obtain a first mixing masterbatch;

[0047] Step 2, add white carbon black, active fluorescent powder, lubricant, and antioxidant to the first mixing masterbatch, and continue mixing treatment at 115℃ for 20 min at a mixing speed of 50 r / min to obtain a second mixing masterbatch;

[0048] Step 3, place the second mixing masterbatch in a vulcanizing machine, add vulcanizing agent and vulcanizing accelerator, and perform vulcanization treatment to obtain a fluorescent sole material.

[0049] In step 3, the temperature of the vulcanization treatment is 165℃, the vulcanization pressure is 15 MPa, and the vulcanization treatment time is 65 min.

[0050] The fluorescent sole material comprises, by weight fraction:

[0051] 43 parts of natural rubber, 24 parts of butadiene rubber, 50 parts of styrene-butadiene rubber, 17 parts of thermoplastic elastomer SBS, 24 parts of white carbon black, 13 parts of active fluorescent powder, 3 parts of lubricant, 2.2 parts of antioxidant, 1.9 parts of vulcanizing agent and 3.6 parts of vulcanizing accelerator.

[0052] In the above, the natural rubber is Indonesian natural rubber SIR-20; the butadiene rubber is BR-9000; the styrene-butadiene rubber is SBR-1502; the thermoplastic elastomer SBS is SBS-T171; the white carbon black is Degussa R-202, with a specific surface area of 100±25 m 2 / g and an average particle size of 14 nm; the lubricant is calcium stearate; the antioxidant is antioxidant MMBZ; the vulcanizing agent is sulfur; and the vulcanizing accelerator is vulcanizing accelerator TMTD.

[0053] The preparation method of the active fluorescent powder comprises:

[0054] S1, mixing and uniformly dispersing blue-green fluorescent powder (brand JCAE) and anhydrous ethanol, then adding γ-aminopropylmethyldiethoxysilane, the mass-volume ratio of the fluorescent powder, γ-aminopropylmethyldiethoxysilane and anhydrous ethanol being 1 g:0.27 g:15 mL, warming to reflux, maintaining stirring for 6 h, then centrifugally separating out the powder, alcohol-washing three times and vacuum drying to obtain aminated fluorescent powder;

[0055] S2, adding 2,3-epoxypropyl acrylate into N,N-dimethylformamide, uniformly stirring, then adding the aminated fluorescent powder, the mass-volume ratio of the aminated fluorescent powder, 2,3-epoxypropyl acrylate and N,N-dimethylformamide being 1 g:0.58 g:25 mL, warming to 70℃ under the protection of nitrogen, maintaining stirring for 8 h, after the reaction is completed, centrifugally separating out the powder, alcohol-washing three times and vacuum drying to obtain acrylated fluorescent powder;

[0056] S3, adding ethylene glycol dimercaptoacetate into N,N-dimethylformamide, uniformly stirring, then introducing nitrogen as a protective gas, adding the acrylated fluorescent powder, the mass-volume ratio of the acrylated fluorescent powder, ethylene glycol dimercaptoacetate and N,N-dimethylformamide being 1 g:1.26 g:25 mL, further adding photosensitizer 659, the amount of which is 5% of the mass of ethylene glycol dimercaptoacetate, under the irradiation of ultraviolet light with an intensity of 250 mW / cm 2 , stirring for 3 h, after the reaction is completed, centrifugally separating out the powder, alcohol-washing three times and vacuum drying to obtain active fluorescent powder.

[0057] Example 2

[0058] A preparation method of an environment-friendly, efficient and long-lasting fluorescent sole material, comprising the following steps:

[0059] Step 1, natural rubber, butadiene rubber, styrene butadiene rubber and thermoplastic elastomer SBS are weighed and placed in a mixer, and mixing treatment is carried out at 128 DEG C for 24 min, and the mixing speed is 60 r / min, to obtain a first mixing masterbatch;

[0060] Step 2, white carbon black, active fluorescent powder, lubricant and antioxidant are added to the first mixing masterbatch, and mixing treatment is continued at 105 DEG C for 25 min, and the mixing speed is 40 r / min, to obtain a second mixing masterbatch;

[0061] Step 3, the second mixing masterbatch is placed in a vulcanizing machine, vulcanizing agent and vulcanizing accelerator are added, and vulcanization treatment is carried out, to obtain a fluorescent sole material.

[0062] In step 3, the temperature of the vulcanization treatment is 155 DEG C, the vulcanization pressure is 20 MPa, and the vulcanization treatment time is 45 min.

[0063] The fluorescent sole material comprises, by weight fraction:

[0064] 32 parts of natural rubber, 18 parts of butadiene rubber, 35 parts of styrene butadiene rubber, 11 parts of thermoplastic elastomer SBS, 16 parts of white carbon black, 8 parts of active fluorescent powder, 2 parts of lubricant, 1.5 parts of antioxidant, 1.3 parts of vulcanizing agent and 2.4 parts of vulcanizing accelerator.

[0065] In the above, the natural rubber is Indonesian natural rubber SIR-10; the butadiene rubber is BR-9001; the styrene butadiene rubber is SBR-1500; the thermoplastic elastomer SBS is SBS-D1116; the white carbon black is Degussa R-106; the lubricant is magnesium stearate; the antioxidant is antioxidant BLE; the vulcanizing agent is sulfur; and the vulcanizing accelerator is vulcanizing accelerator TT.

[0066] The preparation method of the active fluorescent powder comprises:

[0067] S1, the fluorescent powder of sky blue (brand JCBE) is mixed and uniformly dispersed with anhydrous ethanol, then γ-aminopropyl methyl diethoxysilane is added, the mass-volume ratio of the fluorescent powder, γ-aminopropyl methyl diethoxysilane and anhydrous ethanol is 1g:0.18g:10mL, the temperature is raised to reflux, and the powder is separated by centrifugation after 4h of heat preservation and stirring, then the powder is washed with alcohol three times and vacuum dried, to obtain an amino-modified fluorescent powder;

[0068] S2, add 2, 3-epoxypropyl acrylate into N, N-dimethylformamide, stir well, then add amino fluorescent powder, the mass-volume ratio of amino fluorescent powder, 2, 3-epoxypropyl acrylate and N, N-dimethylformamide is 1g: 0.39g: 20ml, heat to 60℃ under the protection of nitrogen, stir for 5h, after the reaction is completed, centrifugal separation of powder, alcohol wash three times, vacuum drying, to get acrylic fluorescent powder;

[0069] S3, add ethylene glycol dimercaptoacetate into N, N-dimethylformamide, stir well, then add nitrogen as protective gas, add acrylic fluorescent powder, the mass-volume ratio of acrylic fluorescent powder, ethylene glycol dimercaptoacetate and N, N-dimethylformamide is 1g: 0.84g: 20ml, then add photosensitizer as photosensitizer 651, the amount is 3% of the mass of ethylene glycol dimercaptoacetate, under the irradiation of ultraviolet light with intensity of 150mW / cm 2 Under the irradiation of ultraviolet light, stir for 5h, after the reaction is completed, centrifugal separation of powder, alcohol wash three times, vacuum drying, to get active fluorescent powder.

[0070] Example 3

[0071] A kind of preparation method of environment-friendly high-efficiency persistent fluorescent sole material, comprising the following steps:

[0072] Step 1, weigh natural rubber, cis-butadiene rubber, styrene-butadiene rubber, thermoplastic elastomer SBS and place them in a mixer, mix at 146℃ for 12min, at a mixing speed of 80r / min, to obtain a first mixing masterbatch;

[0073] Step 2, add white carbon black, active fluorescent powder, lubricant and antioxidant to the first mixing masterbatch, continue to mix at 125℃ for 15min, at a mixing speed of 60r / min, to obtain a second mixing masterbatch;

[0074] Step 3, place the second mixing masterbatch in a vulcanizing machine, add vulcanizing agent and vulcanizing accelerator, and perform vulcanization treatment to obtain a fluorescent sole material.

[0075] In step 3, the vulcanization temperature is 175℃, the vulcanization pressure is 10MPa, and the vulcanization time is 85min.

[0076] Among them, the fluorescent sole material is calculated by weight fraction, including:

[0077] 54 parts of natural rubber, 30 parts of cis-butadiene rubber, 65 parts of styrene-butadiene rubber, 22 parts of thermoplastic elastomer SBS, 32 parts of white carbon black, 18 parts of active fluorescent powder, 4 parts of lubricant, 3 parts of antioxidant, 2.6 parts of vulcanizing agent and 4.8 parts of vulcanizing accelerator.

[0078] In the above, the natural rubber is Indonesian natural rubber SIR-10; the butadiene rubber is BR-9002; the styrene-butadiene rubber SBR-1723; the thermoplastic elastomer SBS is SBS-D1155; the white carbon black is Degussa A-380; the lubricant is zinc stearate; the antioxidant is antioxidant MB; the vulcanizing agent is sulfur; and the vulcanizing accelerator is vulcanizing accelerator DPG.

[0079] The preparation method of the active fluorescent powder comprises the following steps:

[0080] S1, the yellow-green fluorescent powder (JCCE) is mixed and uniformly dispersed with anhydrous ethanol, and then γ-aminopropylmethyldiethoxysilane is added, the mass-volume ratio of the fluorescent powder, the γ-aminopropylmethyldiethoxysilane and the anhydrous ethanol is 1 g:0.36 g:20 mL, the temperature is raised to reflux, and the temperature is kept for 8 hours of stirring, then the powder is separated by centrifugation, washed with alcohol three times, and vacuum dried to obtain the aminated fluorescent powder;

[0081] S2, the 2,3-epoxypropyl acrylate is added to N,N-dimethylformamide, and after being fully stirred and uniformly mixed, the aminated fluorescent powder is added, the mass-volume ratio of the aminated fluorescent powder, the 2,3-epoxypropyl acrylate and the N,N-dimethylformamide is 1 g:0.78 g:30 mL, the temperature is raised to 80 DEG C under the protection of nitrogen, and the temperature is kept for 10 hours of stirring, then the powder is separated by centrifugation after the reaction is completed, washed with alcohol three times, and vacuum dried to obtain the acrylated fluorescent powder;

[0082] S3, the ethylene glycol dimercaptoacetate is added to N,N-dimethylformamide, and after being fully stirred and uniformly mixed, nitrogen is introduced as a protective gas, the acrylated fluorescent powder is added, the mass-volume ratio of the acrylated fluorescent powder, the ethylene glycol dimercaptoacetate and the N,N-dimethylformamide is 1 g:1.68 g:30 mL, the photosensitizer is added as photosensitizer 651, the amount of which is 7% of the mass of the ethylene glycol dimercaptoacetate, and the temperature is raised to 80 DEG C under the protection of nitrogen, and the temperature is kept for 2 hours of stirring, then the powder is separated by centrifugation after the reaction is completed, washed with alcohol three times, and vacuum dried to obtain the active fluorescent powder. 2 Under the irradiation of ultraviolet light, the stirring treatment is carried out for 2 hours, then the powder is separated by centrifugation after the reaction is completed, washed with alcohol three times, and vacuum dried to obtain the active fluorescent powder.

[0083] Comparative Example 1

[0084] A fluorescent sole material, which is different from Example 1 in that the active fluorescent powder in the components of Example 1 is replaced by ordinary blue-green fluorescent powder (JCAE), and the rest of the components and processes are the same as those of Example 1.

[0085] The fluorescent sole material comprises, by weight fraction:

[0086] 43 parts of natural rubber, 24 parts of butadiene rubber, 50 parts of styrene-butadiene rubber, 17 parts of thermoplastic elastomer SBS, 24 parts of white carbon black, 13 parts of fluorescent powder, 3 parts of lubricant, 2.2 parts of antioxidant, 1.9 parts of vulcanizing agent and 3.6 parts of vulcanizing accelerator.

[0087] Comparative Example 2

[0088] A fluorescent sole material, which is different from Example 1 in that the components of the fluorescent sole material are different, the active fluorescent powder in the components is replaced by amino fluorescent powder (prepared the same as S1 of Example 1), and the rest of the components and processes are the same as Example 1.

[0089] The fluorescent sole material includes, by weight fraction:

[0090] 43 parts of natural rubber, 24 parts of butadiene rubber, 50 parts of styrene-butadiene rubber, 17 parts of thermoplastic elastomer SBS, 24 parts of white carbon black, 13 parts of amino fluorescent powder, 3 parts of lubricant, 2.2 parts of antioxidant, 1.9 parts of vulcanizing agent and 3.6 parts of vulcanizing accelerator.

[0091] Comparative Example 3

[0092] A fluorescent sole material, which is different from Example 1 in that the components of the fluorescent sole material are different, the active fluorescent powder in the components is replaced by acrylated fluorescent powder (prepared the same as S2 of Example 1), and the rest of the components and processes are the same as Example 1.

[0093] The fluorescent sole material includes, by weight fraction:

[0094] 43 parts of natural rubber, 24 parts of butadiene rubber, 50 parts of styrene-butadiene rubber, 17 parts of thermoplastic elastomer SBS, 24 parts of white carbon black, 13 parts of acrylated fluorescent powder, 3 parts of lubricant, 2.2 parts of antioxidant, 1.9 parts of vulcanizing agent and 3.6 parts of vulcanizing accelerator.

[0095] Related detection

[0096] The fluorescent sole materials prepared from Example 1 and Comparative Examples 1-3 are detected in performance, including: tensile strength refers to standard GB / T 528-2009; tear strength refers to standard GB / T 529-2008; resilience rate refers to standard GB / T 1681-2009; aging treatment is heat and oxygen aging in an oven at 120℃ for 72h; durability detection is to use a 0.6J energy ultraviolet lamp to irradiate the sole material for 10 seconds, then observe whether discoloration occurs, if discoloration occurs, it does not pass, if no discoloration occurs, it passes; the results are shown in Table 1:

[0097] Table 1 Performance display of different fluorescent sole materials

[0098]

[0099] As can be seen from Table 1, the fluorescent sole material prepared in Embodiment 1 of the present application not only has higher strength, but also has better elasticity, and in particular, the heat-oxygen aging resistance and durability are very excellent, which indicates that the fluorescent sole material obtained by using the method of Embodiment 1 of the present application can be used more durably and stably in a more severe environment.

[0100] In the description of the present specification, the description referring to the terms "one embodiment", "some embodiments", "an example", "a specific example", or "some examples" and the like means that the specific features, structures, materials or characteristics described in connection with the embodiment or example are included in at least one embodiment or example of the present application. In the present specification, the illustrative description of the above terms should not be understood as necessarily referring to the same embodiment or example. Moreover, the specific features, structures, materials or characteristics described can be combined in any one or more embodiments or examples in a suitable manner. In addition, those skilled in the art can combine and integrate different embodiments or examples described in the present specification.

[0101] Although the embodiments of the present application have been shown and described above, it should be understood that the above-described embodiments are exemplary and should not be construed as limiting the present application, and those skilled in the art can make changes, modifications, replacements and variations to the above-described embodiments within the scope of the present application.

Claims

1. A method for preparing an environmentally friendly, highly efficient, and durable fluorescent shoe sole material, characterized in that, Includes the following steps: Step 1: Weigh natural rubber, butadiene rubber, styrene-butadiene rubber and thermoplastic elastomer SBS and place them in a mixing mill for mixing to obtain the first mixing masterbatch; Step 2: Add white carbon black, active phosphor, lubricant and antioxidant to the first mixing masterbatch, and continue mixing to obtain the second mixing masterbatch; Step 3: Place the second compound masterbatch into a vulcanizing machine, add vulcanizing agent and vulcanization accelerator, and carry out vulcanization treatment to obtain fluorescent shoe sole material; The fluorescent sole material, calculated by weight, comprises: 32-54 parts natural rubber, 18-30 parts butadiene rubber, 35-65 parts styrene-butadiene rubber, 11-22 parts thermoplastic elastomer SBS, 16-32 parts silica, 8-18 parts reactive fluorescent powder, 2-4 parts lubricant, 1.5-3 parts antioxidant, 1.3-2.6 parts vulcanizing agent and 2.4-4.8 parts vulcanization accelerator; The preparation method of the active phosphor includes: S1. Mix and disperse the phosphor and anhydrous ethanol evenly, then add γ-aminopropylmethyldiethoxysilane, heat to reflux, keep warm and stir for 4-8 hours, then centrifuge, wash and dry to obtain aminated phosphor; S2. Add 2,3-epoxypropyl acrylate to N,N-dimethylformamide, stir thoroughly, then add aminated phosphor, heat to 60-80℃ under nitrogen protection, keep warm and stir for 5-10 hours. After the reaction is complete, centrifuge, wash and dry to obtain acrylic phosphor. S3. Add ethylene glycol dimercaptoacetate to N,N-dimethylformamide, stir thoroughly, then introduce nitrogen as a protective gas, add acrylic phosphor and photosensitizer, and stir under ultraviolet light for 2-5 hours. After the reaction is complete, centrifuge, wash and dry to obtain active phosphor.

2. The method for preparing an environmentally friendly, efficient, and durable fluorescent shoe sole material according to claim 1, characterized in that, In step 1, the mixing temperature is 128-146℃, the mixing speed is 60-80 r / min, and the mixing time is 12-24 min.

3. The method for preparing an environmentally friendly, efficient, and durable fluorescent shoe sole material according to claim 1, characterized in that, In step 2, the mixing temperature is 105-125℃, the mixing speed is 40-60 r / min, and the mixing time is 15-25 min.

4. In the preparation method of an environmentally friendly, efficient and durable fluorescent shoe sole material according to claim 1, in step 3, the vulcanization temperature is 155-175℃, the vulcanization pressure is 10-20MPa, and the vulcanization time is 45-85min.

5. The method for preparing an environmentally friendly, efficient, and durable fluorescent shoe sole material according to claim 1, characterized in that, The natural rubber is Indonesian natural rubber SIR-10 or Indonesian natural rubber SIR-20; the butadiene rubber is one of BR-9000, BR-9001, and BR-9002; the styrene-butadiene rubber is one of SBR-1500, SBR-1502, SBR-1712, and SBR-1723; and the thermoplastic elastomer SBS is one of SBS-T171, SBS-D1116, SBS-D1102, and SBS-D1155.

6. The method for preparing an environmentally friendly, efficient, and durable fluorescent shoe sole material according to claim 1, characterized in that, The white carbon black is one of Degussa R-202, Degussa R-106, Degussa A-380, and Degussa A-200; the lubricant is one of calcium stearate, magnesium stearate, and zinc stearate; and the antioxidant is one of antioxidant MMBZ, antioxidant BLE, and antioxidant MB.

7. The method for preparing an environmentally friendly, efficient, and durable fluorescent shoe sole material according to claim 1, characterized in that, The vulcanizing agent is sulfur; the vulcanization accelerator is one of the following: TMTD, TT, DPG, and DM.

8. The method for preparing an environmentally friendly, efficient, and durable fluorescent shoe sole material according to claim 1, characterized in that, In S1, the mass-to-volume ratio of phosphor, γ-aminopropylmethyldiethoxysilane, and anhydrous ethanol is 1 g:(0.18-0.36) g:(10-20) mL; in S2, the mass-to-volume ratio of aminated phosphor, 2,3-epoxypropyl acrylate, and N,N-dimethylformamide is 1 g:(0.39-0.78) g:(20-30) mL; in S3, the mass-to-volume ratio of acrylic phosphor, ethylene glycol dimercaptoacetate, and N,N-dimethylformamide is 1 g:(0.84-1.68) g:(20-30) mL.

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