Preparation process of EVA (Ethylene Vinyl Acetate) modified particles, EVA modified particles and application of EVA modified particles

Abstract

The invention relates to the technical field of EVA modified particles, in particular to a preparation technology of EVA modified particles, the EVA modified particles and application of the EVA modified particles, and the EVA modified particles are prepared from, by weight, 35-40 parts of EVA, 10-15 parts of elastomer SEBS, 6-10 parts of titanium dioxide doped additive, 3-5 parts of foaming agent AC, 3-5 parts of cross-linking agent, 4-6 parts of modified zinc oxide agent, 0.3-0.5 part of stearic acid and 0.3-0.5 part of zinc stearate. According to the EVA modified particles, EVA is matched with the elastomer SEBS, meanwhile, the foaming agent AC, the cross-linking agent, the stearic acid and the zinc stearate functional auxiliary agents are added, the added titanium dioxide doped additive and the modified zinc oxide agent serve as blending agents, the EVA modified particles and the blending agents have a synergistic effect, and the prepared EVA modified particles are excellent in skid resistance and elastic performance and good in anti-skid performance. And meanwhile, the product has remarkable bending resistance, wear resistance and stability.

Description

Technical Field

[0001] The invention relates to the technical field of EVA modified particles, and in particular to a preparation process of EVA modified particles, the EVA modified particles and applications thereof. Background Art

[0002] Shoes can generally be divided into soles and uppers. The soles can be further divided into outsoles that are in direct contact with the ground and have a wear-resistant effect, midsoles that mainly play a shock-absorbing role, and insoles that are in direct contact with human feet. The EVA material used for the soles has poor anti-slip properties. In order to improve the anti-slip properties of the product, it is easy to cause low elasticity of the product. At the same time, the product has poor resistance to bending and wear resistance, which further limits the use efficiency of the product. Summary of the invention

[0003] In view of the defects of the prior art, the purpose of the present invention is to provide a preparation process of EVA modified particles, EVA modified particles and applications thereof, so as to solve the problems raised in the above background technology.

[0004] The present invention solves the technical problem by adopting the following technical solution: The present invention provides an EVA modified particle, comprising the following raw materials in parts by weight: EVA 35~40 parts, elastomer SEBS 10~15 parts, additive for titanium dioxide 6~10 parts, foaming agent AC 3~5 parts, cross-linking agent 3~5 parts, modified zinc oxide agent 4~6 parts, stearic acid 0.3~0.5 parts, zinc stearate 0.3~0.5 parts.

[0005] Preferably, the EVA modified particles include the following raw materials in parts by weight: 37.5 parts of EVA, 12.5 parts of elastomer SEBS, 8 parts of additives for blending titanium dioxide, 4 parts of foaming agent AC, 4 parts of cross-linking agent, 5 parts of modified zinc oxide agent, 0.4 parts of stearic acid, and 0.4 parts of zinc stearate.

[0006] Preferably, the VA content in the EVA is less than 15%; the crosslinking agent is crosslinking agent DCP; the elastomer SEBS is composed of non-linear chain structure SEBS and linear chain structure SEBS, wherein the mass percentage of linear chain structure SEBS is 35%.

[0007] Preferably, the preparation method of the additive for mixing titanium dioxide is: S1: Preparation of boron nitride modifier: S11: Stirring the boron nitride uniformly in a sufficient amount of 5% by mass potassium permanganate solution, then washing, filtering and drying to obtain dry boron nitride; preheating the dry boron nitride at 55-60° C. for 1 hour to obtain preheated boron nitride; S12: adding 5 to 8 parts of preheated boron nitride and 3 to 5 parts of magnesium oxide to 5 to 8 parts of sodium silicate solution by weight, and then adding 2 to 3 parts of cerium oxide, stirring, filtering and drying after stirring to obtain a boron nitride modifier; S2: Add 3-5 parts of titanium dioxide and 2-4 parts of barium nitrate solution to 5-8 parts of 5% sodium lignin sulfonate solution by weight, then add 2-3 parts of boron nitride modifier, stir evenly, and obtain a titanium dioxide solution; S3: Mix the titanium dioxide liquid and the additive in a weight ratio of 5:(2~3), and ball mill them at a speed of 1000~1500r / min for 1h. After the ball milling is completed, filter and dry to obtain the additive for titanium dioxide.

[0008] Preferably, the mass fraction of the sodium silicate solution is 5-8%; the mass fraction of the barium nitrate solution is 3-5%; the stirring speed of the stirring treatment in S12 is 550-650 r / min, and the stirring is performed for 20-30 min.

[0009] Preferably, the preparation method of the synergist is: 4-6 parts of calcium sulfate whiskers, 3-5 parts of cordierite and 1-2 parts of silane coupling agent are added to 5-8 parts of sodium dodecylbenzene sulfonate solution by weight, and then 2-3 parts of aluminum oxide are added, stirred sufficiently, and finally filtered and dried to obtain a synergist.

[0010] Preferably, the silane coupling agent is silane coupling agent KH560; the mass fraction of the sodium dodecylbenzene sulfonate solution is 4-6%.

[0011] Preferably, the preparation method of the modified zinc oxide agent is: S1a: placing zinc oxide in a proton irradiation box and irradiating it for 20-30 minutes at an irradiation power of 350-400W, and obtaining irradiated zinc oxide after the irradiation is completed; S1b: adding 3-5 parts of silver nanowires and 1-3 parts of silicon carbide to 5-8 parts of 6% sodium alginate solution by weight, and then adding 2-4 parts of sodium carboxymethyl cellulose, stirring well, to obtain a modified solution; S1c: The irradiated zinc oxide and the modified liquid are subjected to ultrasonic modification treatment in a weight ratio of 5:7, and then filtered and dried to obtain a modified zinc oxide agent; the ultrasonic modification treatment is performed with an ultrasonic power of 400-450 W and the ultrasonic treatment is performed for 1 hour.

[0012] The present invention also provides a preparation process of EVA modified particles, comprising the following steps: The EVA modified particle raw material is weighed according to weight parts, and EVA, elastomer SEBS, additives blended with titanium dioxide, modified zinc oxide, stearic acid and zinc stearate are sent to an internal mixer for internal mixing for 5 minutes at a temperature of 95°C. Subsequently, a foaming agent AC and a cross-linking agent are added, and the internal mixing treatment is continued at a temperature of 110°C for 2 minutes. After the internal mixing is completed, the mixture is opened for refining, granulation is performed, and finally molded for foaming at a molding temperature of 210°C and a molding pressure of 15 MPa for 20 minutes to obtain EVA modified particles.

[0013] The invention also provides application of the EVA modified particles in shoe soles.

[0014] Compared with the prior art, the present invention has the following beneficial effects: The EVA modified particles of the present invention adopt EVA and elastomer SEBS, and at the same time add foaming agent AC, crosslinking agent, stearic acid and zinc stearate functional additives, as well as additives for mixing titanium dioxide and modified zinc oxide as a blending agent. The two are synergistically coordinated to prepare the EVA modified particles with excellent anti-slip and elastic properties, and the product has remarkable bending resistance, wear resistance and stability effects. The additive for titanium dioxide is treated with boron nitride through potassium permanganate solution, and then preheated to improve and optimize its active performance. The boron nitride modifier is prepared by synergistically blending preheated boron nitride, magnesium oxide, sodium silicate solution and cerium oxide. The boron nitride structure is matched with magnesium oxide and cerium oxide raw materials, and is matched with the titanium dioxide liquid system. At the same time, titanium dioxide, barium nitrate solution and other raw materials are auxiliary adjusted. The raw materials are co-matched and synergistic, so that the titanium dioxide liquid and the additive can be better coordinated and synergistic, and jointly improved and optimized. The additive uses calcium sulfate whiskers and cordierite as the matrix, and is matched with raw materials such as aluminum oxide. The whisker-like structure of the whiskers is used to blend cordierite and aluminum oxide into the system, thereby enhancing the functional effect of the additive for titanium dioxide in the system, thereby the performance of the product is coordinated and improved, and the performance stability is further improved; The modified zinc oxide agent is made of zinc oxide that has been irradiated to stimulate its active efficiency. The modified liquid uses silver nanowires, silicon carbide, sodium alginate solution and sodium carboxymethyl cellulose. Through the co-adjustment and assistance between the raw materials, silver nanowires are combined with silicon carbide to improve zinc oxide. The modified zinc oxide agent thus obtained has a better synergistic effect with the additives blended with titanium dioxide, and the performance of the product is further improved. DETAILED DESCRIPTION

[0015] The following is a clear and complete description of the technical solutions in the embodiments of the present invention in conjunction with specific embodiments. 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.

[0016] The EVA modified particles of this embodiment include the following raw materials in parts by weight: EVA 35~40 parts, elastomer SEBS 10~15 parts, additive for titanium dioxide 6~10 parts, foaming agent AC 3~5 parts, cross-linking agent 3~5 parts, modified zinc oxide agent 4~6 parts, stearic acid 0.3~0.5 parts, zinc stearate 0.3~0.5 parts.

[0017] The VA content in the EVA of this embodiment is less than 15%; the crosslinking agent is crosslinking agent DCP; the elastomer SEBS is composed of non-linear chain structure SEBS and linear chain structure SEBS, wherein the mass percentage of linear chain structure SEBS is 35%.

[0018] The preparation method of the additive for mixing titanium dioxide in this embodiment is as follows: S1: Preparation of boron nitride modifier: S11: Stirring the boron nitride uniformly in a sufficient amount of 5% by mass potassium permanganate solution, then washing, filtering and drying to obtain dry boron nitride; preheating the dry boron nitride at 55-60° C. for 1 hour to obtain preheated boron nitride; S12: adding 5 to 8 parts of preheated boron nitride and 3 to 5 parts of magnesium oxide to 5 to 8 parts of sodium silicate solution by weight, and then adding 2 to 3 parts of cerium oxide, stirring, filtering and drying after stirring to obtain a boron nitride modifier; S2: Add 3-5 parts of titanium dioxide and 2-4 parts of barium nitrate solution to 5-8 parts of 5% sodium lignin sulfonate solution by weight, then add 2-3 parts of boron nitride modifier, stir evenly, and obtain a titanium dioxide solution; S3: Mix the titanium dioxide liquid and the additive in a weight ratio of 5:(2~3), and ball mill them at a speed of 1000~1500r / min for 1h. After the ball milling is completed, filter and dry to obtain the additive for titanium dioxide.

[0019] The mass fraction of the sodium silicate solution in this embodiment is 5-8%; the mass fraction of the barium nitrate solution is 3-5%; the stirring speed of the stirring treatment in S12 is 550-650 r / min, and the stirring is performed for 20-30 min.

[0020] The preparation method of the synergist of this embodiment is: 4-6 parts of calcium sulfate whiskers, 3-5 parts of cordierite and 1-2 parts of silane coupling agent are added to 5-8 parts of sodium dodecylbenzene sulfonate solution by weight, and then 2-3 parts of aluminum oxide are added, stirred sufficiently, and finally filtered and dried to obtain a synergist.

[0021] The silane coupling agent of the present embodiment is silane coupling agent KH560; the mass fraction of the sodium dodecylbenzene sulfonate solution is 4-6%.

[0022] The preparation method of the modified zinc oxide agent of this embodiment is: S1a: placing zinc oxide in a proton irradiation box and irradiating it for 20-30 minutes at an irradiation power of 350-400W, and obtaining irradiated zinc oxide after the irradiation is completed; S1b: adding 3-5 parts of silver nanowires and 1-3 parts of silicon carbide to 5-8 parts of 6% sodium alginate solution by weight, and then adding 2-4 parts of sodium carboxymethyl cellulose, stirring well, to obtain a modified solution; S1c: The irradiated zinc oxide and the modified liquid are subjected to ultrasonic modification treatment in a weight ratio of 5:7, and then filtered and dried to obtain a modified zinc oxide agent; the ultrasonic modification treatment is performed with an ultrasonic power of 400-450 W and the ultrasonic treatment is performed for 1 hour.

[0023] A preparation process of EVA modified particles of this embodiment comprises the following steps: The EVA modified particle raw material is weighed according to weight parts, and EVA, elastomer SEBS, additives blended with titanium dioxide, modified zinc oxide, stearic acid and zinc stearate are sent to an internal mixer for internal mixing for 5 minutes at a temperature of 95°C. Subsequently, a foaming agent AC and a cross-linking agent are added, and the internal mixing treatment is continued at a temperature of 110°C for 2 minutes. After the internal mixing is completed, the mixture is opened for refining, granulation is performed, and finally molded for foaming at a molding temperature of 210°C and a molding pressure of 15 MPa for 20 minutes to obtain EVA modified particles.

[0024] The invention also provides application of the EVA modified particles in shoe soles.

[0025] Embodiment 1: An EVA modified particle comprises the following raw materials in parts by weight: EVA 35 parts, elastomer SEBS 10 parts, additive for blending titanium dioxide 6 parts, foaming agent AC 3 parts, cross-linking agent 3 parts, modified zinc oxide agent 4 parts, stearic acid 0.3 parts, zinc stearate 0.3 parts.

[0026] The VA content in the EVA of this embodiment is less than 15%; the crosslinking agent is crosslinking agent DCP; the elastomer SEBS is composed of non-linear chain structure SEBS and linear chain structure SEBS, wherein the mass percentage of linear chain structure SEBS is 35%.

[0027] The preparation method of the additive for mixing titanium dioxide in this embodiment is as follows: S1: Preparation of boron nitride modifier: S11: Stir the boron nitride in a sufficient amount of 5% by mass potassium permanganate solution, then wash with water, filter and dry to obtain dry boron nitride; preheat the dry boron nitride at 55° C. for 1 hour to obtain preheated boron nitride; S12: adding 5 parts of preheated boron nitride and 3 parts of magnesium oxide to 5 parts of sodium silicate solution by weight, and then adding 2 parts of cerium oxide, stirring, filtering and drying after stirring to obtain a boron nitride modifier; S2: Add 3 parts of titanium dioxide and 2 parts of barium nitrate solution to 5 parts of 5% sodium lignin sulfonate solution by weight, then add 2 parts of boron nitride modifier, stir evenly, and obtain a titanium dioxide solution; S3: Mix the titanium dioxide liquid and the additive in a weight ratio of 5:2, and perform ball milling at a speed of 1000 r / min for 1 h. After the ball milling is completed, filter and dry to obtain the additive for titanium dioxide.

[0028] The mass fraction of the sodium silicate solution is 5%; the mass fraction of the barium nitrate solution is 3%; the stirring speed of the stirring treatment in S12 is 550 r / min, and the stirring is for 20 minutes.

[0029] The preparation method of the synergist of this embodiment is: 4 parts of calcium sulfate whiskers, 3 parts of cordierite and 1 part of silane coupling agent were added to 5 parts of sodium dodecylbenzene sulfonate solution by weight, and then 2 parts of aluminum oxide were added, stirred sufficiently, and finally filtered and dried to obtain a synergist.

[0030] The silane coupling agent in this embodiment is silane coupling agent KH560; the mass fraction of the sodium dodecylbenzene sulfonate solution is 4%.

[0031] The preparation method of the modified zinc oxide agent of this embodiment is: S1a: placing zinc oxide in a proton irradiation box and irradiating it for 20 minutes at an irradiation power of 350 W, and then completing the irradiation to obtain irradiated zinc oxide; S1b: adding 3 parts of silver nanowires and 1 part of silicon carbide to 5 parts of 6% sodium alginate solution by weight, and then adding 2 parts of sodium carboxymethyl cellulose, stirring well, to obtain a modified solution; S1c: The irradiated zinc oxide and the modified liquid are subjected to ultrasonic modification treatment in a weight ratio of 5:7, and then filtered and dried to obtain a modified zinc oxide agent; the ultrasonic modification treatment is performed at an ultrasonic power of 400 W and the ultrasonic treatment is performed for 1 hour.

[0032] A preparation process of EVA modified particles of this embodiment comprises the following steps: The EVA modified particle raw material is weighed according to weight parts, and EVA, elastomer SEBS, additives blended with titanium dioxide, modified zinc oxide, stearic acid and zinc stearate are sent to an internal mixer for internal mixing for 5 minutes at a temperature of 95°C. Subsequently, a foaming agent AC and a cross-linking agent are added, and the internal mixing treatment is continued at a temperature of 110°C for 2 minutes. After the internal mixing is completed, the mixture is opened for refining, granulation is performed, and finally molded for foaming at a molding temperature of 210°C and a molding pressure of 15 MPa for 20 minutes to obtain EVA modified particles.

[0033] The invention also provides application of the EVA modified particles in shoe soles.

[0034] Embodiment 2: An EVA modified particle comprises the following raw materials in parts by weight: EVA 40 parts, elastomer SEBS 15 parts, additive for blending titanium dioxide 10 parts, foaming agent AC 5 parts, cross-linking agent 5 parts, modified zinc oxide agent 6 parts, stearic acid 0.5 parts, zinc stearate 0.5 parts.

[0035] The VA content in the EVA of this embodiment is less than 15%; the crosslinking agent is crosslinking agent DCP; the elastomer SEBS is composed of non-linear chain structure SEBS and linear chain structure SEBS, wherein the mass percentage of linear chain structure SEBS is 35%.

[0036] The preparation method of the additive for mixing titanium dioxide in this embodiment is as follows: S1: Preparation of boron nitride modifier: S11: Stirring the boron nitride uniformly in a sufficient amount of 5% by mass potassium permanganate solution, then washing, filtering and drying to obtain dry boron nitride; preheating the dry boron nitride at 60° C. for 1 hour to obtain preheated boron nitride; S12: adding 8 parts of preheated boron nitride and 5 parts of magnesium oxide to 8 parts of sodium silicate solution by weight, and then adding 3 parts of cerium oxide, stirring, filtering and drying after stirring to obtain a boron nitride modifier; S2: Add 5 parts of titanium dioxide and 4 parts of barium nitrate solution to 8 parts of 5% sodium lignin sulfonate solution by weight, then add 3 parts of boron nitride modifier, stir evenly, and obtain a titanium dioxide solution; S3: Mix the titanium dioxide liquid and the additive in a weight ratio of 5:3, and ball-mill them at a speed of 1500 r / min for 1 hour. After the ball milling is completed, filter and dry to obtain the additive for titanium dioxide.

[0037] The mass fraction of the sodium silicate solution is 8%; the mass fraction of the barium nitrate solution is 5%; the stirring speed of the stirring treatment in S12 is 650 r / min, and the stirring is for 30 minutes.

[0038] The preparation method of the synergist of this embodiment is: 6 parts of calcium sulfate whiskers, 5 parts of cordierite and 2 parts of silane coupling agent were added to 8 parts of sodium dodecylbenzene sulfonate solution by weight, and then 3 parts of aluminum oxide were added, stirred thoroughly, and finally filtered and dried to obtain a synergist.

[0039] The silane coupling agent in this embodiment is silane coupling agent KH560; the mass fraction of the sodium dodecylbenzene sulfonate solution is 6%.

[0040] The preparation method of the modified zinc oxide agent of this embodiment is: S1a: placing zinc oxide in a proton irradiation box and irradiating it for 30 minutes at an irradiation power of 400 W, and obtaining irradiated zinc oxide after the irradiation is completed; S1b: adding 5 parts of silver nanowires and 3 parts of silicon carbide to 8 parts of 6% sodium alginate solution by weight, and then adding 4 parts of sodium carboxymethyl cellulose, stirring well, to obtain a modified solution; S1c: The irradiated zinc oxide and the modified liquid are subjected to ultrasonic modification at a weight ratio of 5:7, and then filtered and dried to obtain a modified zinc oxide agent; the ultrasonic modification treatment is performed at an ultrasonic power of 450 W and the ultrasonic treatment is performed for 1 hour.

[0041] A preparation process of EVA modified particles of this embodiment comprises the following steps: The EVA modified particle raw material is weighed according to weight parts, and EVA, elastomer SEBS, additives blended with titanium dioxide, modified zinc oxide, stearic acid and zinc stearate are sent to an internal mixer for internal mixing for 5 minutes at a temperature of 95°C. Subsequently, a foaming agent AC and a cross-linking agent are added, and the internal mixing treatment is continued at a temperature of 110°C for 2 minutes. After the internal mixing is completed, the mixture is opened for refining, granulation is performed, and finally molded for foaming at a molding temperature of 210°C and a molding pressure of 15 MPa for 20 minutes to obtain EVA modified particles.

[0042] The invention also provides application of the EVA modified particles in shoe soles.

[0043] Embodiment 3: An EVA modified particle comprises the following raw materials in parts by weight: 37.5 parts of EVA, 12.5 parts of elastomer SEBS, 8 parts of additives for blending titanium dioxide, 4 parts of foaming agent AC, 4 parts of cross-linking agent, 5 parts of modified zinc oxide agent, 0.4 parts of stearic acid, and 0.4 parts of zinc stearate.

[0044] The VA content in the EVA of this embodiment is less than 15%; the crosslinking agent is crosslinking agent DCP; the elastomer SEBS is composed of non-linear chain structure SEBS and linear chain structure SEBS, wherein the mass percentage of linear chain structure SEBS is 35%.

[0045] The preparation method of the additive for mixing titanium dioxide in this embodiment is as follows: S1: Preparation of boron nitride modifier: S11: Stir the boron nitride in a sufficient amount of 5% by mass potassium permanganate solution, then wash with water, filter and dry to obtain dry boron nitride; preheat the dry boron nitride at 57.5°C for 1 hour to obtain preheated boron nitride; S12: adding 6.5 parts of preheated boron nitride and 4 parts of magnesium oxide to 6.5 parts of sodium silicate solution by weight, and then adding 2.5 parts of cerium oxide, stirring, filtering and drying after stirring to obtain a boron nitride modifier; S2: Add 4 parts of titanium dioxide and 3 parts of barium nitrate solution to 6.5 parts of 5% sodium lignin sulfonate solution by weight, then add 2.5 parts of boron nitride modifier, stir evenly, and obtain a titanium dioxide solution; S3: Mix the titanium dioxide liquid and the additive in a weight ratio of 5:2.5, and perform ball milling at a ball milling speed of 1250 r / min for 1 h. After the ball milling is completed, filter and dry to obtain the additive for titanium dioxide.

[0046] The mass fraction of the sodium silicate solution in this embodiment is 5-8%; the mass fraction of the barium nitrate solution is 3-5%; the stirring speed of the stirring treatment in S12 is 550-650 r / min, and the stirring is performed for 20-30 min.

[0047] The preparation method of the synergist of this embodiment is: 5 parts of calcium sulfate whiskers, 4 parts of cordierite and 1.5 parts of silane coupling agent were added to 6.5 parts of sodium dodecylbenzene sulfonate solution by weight, and then 2.5 parts of aluminum oxide were added, stirred thoroughly, and finally filtered and dried to obtain a synergist.

[0048] The silane coupling agent in this embodiment is silane coupling agent KH560; the mass fraction of the sodium dodecylbenzene sulfonate solution is 5%.

[0049] The preparation method of the modified zinc oxide agent of this embodiment is: S1a: placing zinc oxide in a proton irradiation box and irradiating it for 25 minutes at an irradiation power of 375 W, and then completing the irradiation to obtain irradiated zinc oxide; S1b: adding 4 parts of silver nanowires and 2 parts of silicon carbide to 6.5 parts of 6% sodium alginate solution by weight, and then adding 3 parts of sodium carboxymethyl cellulose, stirring well, to obtain a modified solution; S1c: The irradiated zinc oxide and the modified liquid are subjected to ultrasonic modification treatment in a weight ratio of 5:7, and then filtered and dried to obtain a modified zinc oxide agent; the ultrasonic modification treatment is performed at an ultrasonic power of 425 W and the ultrasonic treatment is performed for 1 hour.

[0050] A preparation process of EVA modified particles of this embodiment comprises the following steps: The EVA modified particle raw material is weighed according to weight parts, and EVA, elastomer SEBS, additives blended with titanium dioxide, modified zinc oxide, stearic acid and zinc stearate are sent to an internal mixer for internal mixing for 5 minutes at a temperature of 95°C. Subsequently, a foaming agent AC and a cross-linking agent are added, and the internal mixing treatment is continued at a temperature of 110°C for 2 minutes. After the internal mixing is completed, the mixture is opened for refining, granulation is performed, and finally molded for foaming at a molding temperature of 210°C and a molding pressure of 15 MPa for 20 minutes to obtain EVA modified particles.

[0051] The invention also provides application of the EVA modified particles in shoe soles.

[0052] Comparative Example 1: The difference from Example 3 is that no additive for blending titanium dioxide is added.

[0053] Comparative Example 2: The difference from Example 3 is that no titanium dioxide liquid is added in the preparation of the additive for titanium dioxide.

[0054] Comparative Example 3: The difference from Example 3 is that no boron nitride modifier is added in the preparation of the titanium dioxide solution.

[0055] Comparative Example 4: The difference from Example 3 is that no preheated boron nitride is added in the preparation of the boron nitride modifier.

[0056] Comparative Example 5: The difference from Example 3 is that magnesium oxide and cerium oxide are not added in the preparation of the boron nitride modifier.

[0057] Comparative Example 6: The difference from Example 3 is that no titanium dioxide and barium nitrate solution are added in the preparation of the titanium dioxide solution.

[0058] Comparative Example 7: The difference from Example 3 is that no synergist is added in the preparation of the additive for blending titanium dioxide.

[0059] Comparative Example 8: The difference from Example 3 is that no modified zinc oxide agent is added.

[0060] Comparative Example 9: The difference from Example 3 is that no modifying liquid is added in the preparation of the modified zinc oxide agent.

[0061] Comparative Example 10: The difference from Example 3 is that no silver nanowires or silicon carbide are added to the modified solution.

[0062] The products of Examples 1 to 3 and Comparative Examples 1 to 10 were tested for anti-slip properties and elastic properties under normal conditions and under bending and wear resistance conditions. The bending and wear resistance conditions were to scrape the product 50 times with a load of 10N and then bend it 500 times. The test results are shown in Table 1.

[0063] Table 1 Product performance test results of Examples 1 to 3 and Comparative Examples 1 to 10: It can be seen from comparative examples 1 to 10 and examples 1 to 3 that the product of example 3 has excellent elasticity and anti-slip properties, and the performance can be coordinated and improved. In addition, the product still has excellent performance stability under bending resistance and wear resistance conditions; It can be seen from Comparative Examples 1 to 10 and Example 3 that the performance of the products has a significant trend of deterioration when no additives for mixing titanium dioxide and no modified zinc oxide are added to the products. The performance effect of the products is significant when the two additives are coordinated and synergistic. The performance of the products showed a trend of deterioration to varying degrees when no titanium dioxide liquid was added to the preparation of the titanium dioxide liquid, no boron nitride modifier was added to the preparation of the boron nitride modifier, no preheated boron nitride was added to the preparation of the boron nitride modifier, no magnesium oxide and cerium oxide were added to the preparation of the boron nitride modifier, no titanium dioxide and barium nitrate solution were added to the preparation of the titanium dioxide liquid, and no synergist was added to the preparation of the titanium dioxide additive. In addition, the performance of the products deteriorated significantly when no synergist was added. The boron nitride modifier obtained by the specific method of the present invention is combined with titanium dioxide, barium nitrate solution and other specific processes to prepare the additive for mixing titanium dioxide, and the performance effect of the product is the most significant; In addition, when no modifying liquid is added in the preparation of the modified zinc oxide agent, and silver nanowires and silicon carbide are not added to the modifying liquid, the performance of the product tends to deteriorate. The modified zinc oxide agent improved by the modifying liquid obtained by the specific method of the present invention has the most significant performance effect of the product.

[0064] Based on the fact that additives can significantly change the performance of products, further research is conducted on this.

[0065] Experimental Example 1: The only difference from Example 3 is that no calcium sulfate whiskers are added to the synergist.

[0066] Experimental Example 2: The only difference from Example 3 is that cordierite is not added to the additive.

[0067] Experimental Example 3: The only difference from Example 3 is that no alumina is added to the synergist.

[0068] Experimental Example 4: The only difference from Example 3 is that no silane coupling agent is added to the additive and the sodium dodecylbenzene sulfonate solution is replaced by water.

[0069] The products of Experimental Examples 1 to 4 were tested for anti-slip properties and elastic properties under normal conditions and flexure resistance and wear resistance conditions. The flexure resistance and wear resistance conditions were to scrape the product 50 times with a load of 10N and then flex it 500 times. The test results are shown in Table 2.

[0070] Table 2 Product performance test results of Experimental Examples 1 to 4: It can be seen from Experimental Examples 1-4 that when calcium sulfate whiskers are not added to the additive, the performance of the product has a large trend of change. At the same time, when cordierite, alumina, and silane coupling agent are not added to the additive, and the sodium dodecylbenzene sulfonate solution is replaced by water, the performance of the product has a trend of deterioration. The additive obtained by the specific method of the present invention has the most significant performance effect of the product, and the effects of other methods are not as obvious as those of the present invention.

[0071] It will be apparent to those skilled in the art that the present invention is not limited to the details of the exemplary embodiments described above and that the present invention can be implemented in other specific forms without departing from the spirit or essential features of the present invention. Therefore, the embodiments should be considered exemplary and non-restrictive in all respects, and the scope of the present invention is defined by the appended claims rather than the above description, and it is intended that all changes falling within the meaning and scope of the equivalent elements of the claims be included in the present invention.

[0072] In addition, it should be understood that although the present specification is described according to implementation modes, not every implementation mode contains only one independent technical solution. This description of the specification is only for the sake of clarity. Those skilled in the art should regard the specification as a whole. The technical solutions in each embodiment may also be appropriately combined to form other implementation modes that can be understood by those skilled in the art.

Claims

1. An EVA modified particle, characterized in that: It includes the following raw materials in parts by weight: EVA 35-40 parts, elastomer SEBS 10-15 parts, additive for titanium dioxide 6-10 parts, foaming agent AC 3-5 parts, crosslinking agent 3-5 parts, modified zinc oxide 4-6 parts, stearic acid 0.3-0.5 parts, zinc stearate 0.3-0.5 parts; The preparation method of the additive for mixing titanium dioxide is as follows: S1: Preparation of boron nitride modifier: S11: Stirring the boron nitride uniformly in a sufficient amount of 5% by mass potassium permanganate solution, then washing, filtering and drying to obtain dry boron nitride; preheating the dry boron nitride at 55-60° C. for 1 hour to obtain preheated boron nitride; S12: adding 5 to 8 parts of preheated boron nitride and 3 to 5 parts of magnesium oxide to 5 to 8 parts of sodium silicate solution by weight, and then adding 2 to 3 parts of cerium oxide, stirring, filtering and drying after stirring to obtain a boron nitride modifier; S2: Add 3-5 parts of titanium dioxide and 2-4 parts of barium nitrate solution to 5-8 parts of 5% sodium lignin sulfonate solution by weight, then add 2-3 parts of boron nitride modifier, stir evenly, and obtain a titanium dioxide solution; S3: Mix the titanium dioxide solution and the additive in a weight ratio of 5:(2-3), and ball mill the mixture at a speed of 1000-1500 r / min for 1 h. After the ball milling is completed, filter and dry the mixture to obtain the additive for titanium dioxide; The preparation method of the modified zinc oxide agent is: S1a: placing zinc oxide in a proton irradiation box and irradiating it for 20-30 minutes at an irradiation power of 350-400W, and obtaining irradiated zinc oxide after the irradiation is completed; S1b: adding 3-5 parts of silver nanowires and 1-3 parts of silicon carbide to 5-8 parts of 6% sodium alginate solution by weight, and then adding 2-4 parts of sodium carboxymethyl cellulose, stirring sufficiently to obtain a modified solution; S1c: subjecting the irradiated zinc oxide and the modified liquid to ultrasonic modification treatment in a weight ratio of 5:7, and then filtering and drying to obtain a modified zinc oxide agent.

2. The EVA modified particles according to claim 1, characterized in that The EVA modified particles include the following raw materials in parts by weight: 37.5 parts of EVA, 12.5 parts of elastomer SEBS, 8 parts of additives for blending titanium dioxide, 4 parts of foaming agent AC, 4 parts of cross-linking agent, 5 parts of modified zinc oxide agent, 0.4 parts of stearic acid, and 0.4 parts of zinc stearate.

3. The EVA modified particles according to claim 1, characterized in that The VA content in the EVA is less than 15%; the crosslinking agent is crosslinking agent DCP; the elastomer SEBS is composed of non-linear chain structure SEBS and linear chain structure SEBS, wherein the mass percentage of the linear chain structure SEBS is 35%.

4. The EVA modified particles according to claim 1, characterized in that The mass fraction of the sodium silicate solution is 5-8%; the mass fraction of the barium nitrate solution is 3-5%.

5. The EVA modified particles according to claim 1, characterized in that: The stirring speed of the stirring treatment in S12 is 550~650r / min, and the stirring is performed for 20~30min.

6. The EVA modified particles according to claim 1, characterized in that: The preparation method of the synergist is: 4-6 parts of calcium sulfate whiskers, 3-5 parts of cordierite and 1-2 parts of silane coupling agent are added to 5-8 parts of sodium dodecylbenzene sulfonate solution by weight, and then 2-3 parts of aluminum oxide are added, stirred sufficiently, and finally filtered and dried to obtain a synergist.

7. The EVA modified particles according to claim 6, characterized in that: The silane coupling agent is silane coupling agent KH560; the mass fraction of the sodium dodecylbenzene sulfonate solution is 4-6%.

8. The EVA modified particles according to claim 1, characterized in that: The ultrasonic power of the ultrasonic modification treatment in S1c was 400~450W, and the ultrasonic treatment was for 1h.

9. A process for preparing EVA modified particles, for preparing the EVA modified particles according to any one of claims 1 to 8, characterized in that: The following steps are involved: The EVA modified particle raw material is weighed according to weight parts, and EVA, elastomer SEBS, additives blended with titanium dioxide, modified zinc oxide, stearic acid and zinc stearate are sent to an internal mixer for internal mixing for 5 minutes at a temperature of 95°C. Subsequently, a foaming agent AC and a cross-linking agent are added, and the internal mixing treatment is continued at a temperature of 110°C for 2 minutes. After the internal mixing is completed, the mixture is opened for refining, granulation is performed, and finally molded for foaming at a molding temperature of 210°C and a molding pressure of 15 MPa for 20 minutes to obtain EVA modified particles.

10. Use of the EVA modified particles according to any one of claims 1 to 8 in shoe soles.

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