Deodorizing high-toughness sole material and preparation method thereof

Abstract

The invention discloses an odor-resistant high-toughness sole material and a preparation method thereof, and relates to the technical field of high polymer material preparation. The odor-resistant high-toughness sole material is prepared from the following components in parts by mass: 80 to 100 parts of matrix resin, 5 to 10 parts of a composite odor-resistant agent, 10 to 25 parts of a toughening agent, 20 to 40 parts of a filling agent, 2 to 5 parts of a cross-linking agent and 0.5 to 1.5 parts of an anti-aging agent. The antibacterial agent with a specific structure is compounded with the adsorbent, so that a dual mechanism of bacteriostasis and deodorization is realized. The antibacterial agent inhibits bacterium breeding from the source to prevent peculiar smell from being generated, the adsorbent rapidly captures existing peculiar smell molecules, the synergistic effect overcomes the defects that a traditional single deodorization component is prone to loss and saturation and short in effect duration time, and the deodorization durability and comprehensive effect are remarkably improved.

Description

Technical Field

[0001] This invention relates to the field of polymer material preparation technology, specifically to an odor-resistant and high-toughness shoe sole material and its preparation method. Background Technology

[0002] As a core component of footwear, the material properties of the sole directly determine the wearing experience, lifespan, and comfort of the footwear. Currently, most sole materials on the market are based on polymers such as ethylene-vinyl acetate copolymer, thermoplastic elastomers, and styrene-butadiene rubber. Although these materials can meet basic requirements for wear resistance and support, there are still many problems that need to be solved in practical applications.

[0003] On the one hand, during the wearing process, the enclosed space in contact with the feet on the sole is prone to the growth of bacteria and mold. These microorganisms decompose the organic matter in sweat and produce odor. Although some existing sole materials have added single antibacterial agents or adsorbents, they have the problems of single odor-proof effect and short duration. Antibacterial agents are easy to lose and adsorbents are easy to saturate, making it difficult to achieve long-term odor prevention. On the other hand, conventional sole materials often sacrifice toughness in order to balance hardness and wear resistance. They are prone to cracking and deformation under complex stress conditions such as bending and pressure, which reduces the service life of the sole. On the other hand, simply adding toughening agents can easily lead to a decrease in the overall strength of the material and a deterioration in its formability.

[0004] Therefore, developing a shoe sole material that combines odor resistance and high toughness with a stable manufacturing process to solve the technical pain points of poor odor resistance and insufficient toughness in existing products, and to meet consumers' needs for comfortable, durable, and odorless footwear, has become an urgent research direction in the field of polymer shoe sole materials. Summary of the Invention

[0005] The purpose of this invention is to address the problems of existing shoe sole materials having a single odor-resistant effect with short duration, insufficient toughness, and susceptibility to cracking and deformation. This invention provides an odor-resistant, high-toughness shoe sole material and its preparation method. This material aims to achieve a good combination of long-lasting odor resistance and high toughness, and has excellent processing stability and comprehensive performance, in order to meet the market demand for comfortable, durable, and odorless footwear.

[0006] To achieve the above objectives, the technical solution adopted by the present invention is: an odor-resistant and high-toughness shoe sole material, comprising the following components by weight: 80-100 parts of matrix resin, 5-10 parts of composite odor-resistant agent, 10-25 parts of toughening agent, 20-40 parts of filler, 2-5 parts of crosslinking agent, and 0.5-1.5 parts of anti-aging agent; The composite deodorant is composed of an antibacterial agent and an adsorbent, with a mass ratio of 1:(1-3). The antibacterial agent is a compound shown below: ; Substituents in the compound Selected from: any one of fluorine, hydroxyl, trifluoromethyl, and nitro; The adsorbent is one or more of bamboo charcoal powder, diatomaceous earth, and activated carbon.

[0007] Furthermore, the antibacterial agent is any one of the following compounds: ; .

[0008] Furthermore, the matrix resin is one or more of ethylene-vinyl acetate copolymer, thermoplastic elastomer, and styrene-butadiene rubber.

[0009] Furthermore, the toughening agent is one or more of ethylene-octene copolymer, polybutadiene rubber, and maleic anhydride-grafted PE.

[0010] Furthermore, the filler is one or more of silica, calcium carbonate, and talc.

[0011] Furthermore, the crosslinking agent is dicumyl peroxide.

[0012] Furthermore, the antioxidant is one or more of antioxidant 1010, antioxidant 168, and antioxidant RD.

[0013] Furthermore, the odor-resistant and high-toughness sole material may also contain vinyl elastomers, ethylene-vinyl alcohol copolymers, and highly branched polyolefins.

[0014] A method for preparing an odor-resistant and high-toughness shoe sole material includes the following steps: S1. Pretreatment: Place the adsorbent in the composite deodorant in a drying oven and dry it at 80-105℃ for 2-4 hours to remove moisture from the adsorbent. After cooling to room temperature, mix it evenly with the antibacterial agent to obtain the composite deodorant for later use; pulverize the filler to 200-400 mesh for later use. S2. Mixing: The matrix resin and antioxidant are put into an internal mixer and mixed at 120-140℃ and 30-50r / min for 5-8min until the material is melted and uniform; then the toughening agent and filler are added in sequence, and the mixing is continued for 10-15min to obtain the primary compound. S3. Secondary mixing: Add the prepared composite deodorizing agent and crosslinking agent to the primary mixture, adjust the internal mixer temperature to 130-150℃ and the speed to 40-60r / min, and continue mixing for 8-12min to ensure that each component is evenly dispersed and to obtain a uniform mixed material. S4. Plasticizing extrusion: The compounded material is fed into an extruder, and the temperature of each section of the extruder is controlled as follows: feeding section 110-125℃, compression section 130-145℃, homogenization section 145-155℃, and die head 150-160℃. The extrusion speed is 5-10m / min. After extrusion, the material is cooled, shaped, and granulated to obtain shoe sole material granules. S5. Compression molding: The shoe sole material particles are placed into a shoe sole mold and molded at 150-160℃ and 10-15MPa for 8-12 minutes. Then, the material is demolded and cooled to room temperature to obtain an odor-resistant and high-toughness shoe sole material.

[0015] Furthermore, in step S1, the moisture content of the dried adsorbent is ≤0.5%, and a high-speed mixer is used when mixing the antibacterial agent and the adsorbent, with a mixing speed of 800-1200 r / min and a mixing time of 15-20 min.

[0016] Furthermore, in step S2, the feeding sequence of the internal mixer is as follows: first add the matrix resin and antioxidant, then add the toughening agent after melting, and finally add the filler after stirring evenly, so as to avoid the filler agglomerating and affecting the mixing effect.

[0017] Furthermore, in step S5, the finished shoe sole after demolding needs to be placed in a constant temperature drying oven and kept at 60-80℃ for 2-3 hours to eliminate internal stress and further improve the toughness and dimensional stability of the shoe sole.

[0018] This invention, through the precise proportioning and synergistic effect of its various formulation components, fundamentally solves the core technical problems of poor odor control and insufficient toughness in existing shoe sole materials, while also considering material processing stability and overall performance. The matrix resin uses high-molecular materials such as ethylene-vinyl acetate copolymer and thermoplastic elastomers as a base, ensuring the support and wear resistance of the sole. The toughening agent is compatible with the matrix resin and forms a flexible phase in the system, compensating for the defect of conventional shoe sole materials sacrificing toughness for hardness, effectively improving the material's bending and compressive strength, preventing cracking and deformation. Furthermore, the crosslinking agent dicumyl peroxide enables appropriate crosslinking of the resin system, improving toughness while preventing a decrease in overall strength due to the simple addition of toughening agents. The composite odor deodorizer uses a combination of a specific structured antibacterial agent and adsorbents such as bamboo charcoal powder. The antibacterial agent can effectively inhibit the growth of bacteria and fungi on the feet, preventing odor generation at its source, while the adsorbent can quickly adsorb existing odor molecules. This synergistic approach achieves a dual deodorizing effect of both antibacterial and odor-eliminating properties, solving the problems of single deodorizing components having limited effectiveness, short duration, easy loss of antibacterial agents, and easy saturation of adsorbents. The filler, after being pulverized, is mixed with the other components, which not only improves the material's formability and mechanical properties but also avoids the problem of uneven dispersion caused by large-particle fillers. The anti-aging agent can delay the aging of the material during use and processing, ensuring the long-term performance stability of the sole. The precise control of the mass ratio of each component ensures that the functions of deodorization, toughening, forming, and wear resistance are compatible with each other without mutual antagonism. Ultimately, this achieves a good combination of long-lasting deodorization and high toughness in the sole material, while solving performance problems derived from the preparation process, such as uneven component dispersion and filler agglomeration.

[0019] Compared with the prior art, the beneficial effects of the present invention are: 1. Dual Synergistic Odor Control: By combining a specially structured antibacterial agent with an adsorbent, a dual mechanism of antibacterial action and odor removal is achieved. The antibacterial agent inhibits bacterial growth at the source to prevent odor generation, while the adsorbent quickly captures existing odor molecules. This synergistic effect overcomes the shortcomings of traditional single odor-control components, such as easy loss, easy saturation, and short duration of effect, significantly improving the durability and overall effectiveness of odor control.

[0020] 2. Good balance between toughness and strength: Through the compatibility design of toughening agent and matrix resin, and the moderate cross-linking achieved by cross-linking agent, the technical pain point of conventional materials sacrificing toughness in order to achieve hardness is effectively made up for. It significantly improves the bending, compressive strength and elongation at break of the material, while avoiding the overall strength reduction caused by the addition of toughening agent, and greatly reduces the risk of cracking and deformation of the sole under complex stress conditions. Attached Figure Description

[0021] Figure 1 This is the NMR spectrum of the antibacterial agent 1 described in this invention. Detailed Implementation

[0022] The technical solution of the present invention will now be clearly and completely described with reference to the accompanying drawings. Obviously, the described embodiments are merely some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention.

[0023] Preparation Example 1 Preparation of antibacterial agent 1: ; Under nitrogen protection, 5.00 g of raw material 1 and 5.63 g of raw material 2 were added sequentially to the reaction flask, followed by 80 mL of anhydrous ethyl acetate. Stirring was initiated to form a homogeneous suspension. Then, 20.7 mL of N,N-diisopropylethylamine was added in one syringe. The reaction flask was placed in an ice-water bath to cool to approximately 0°C. 58.9 mL of a 50 wt% T3P ethyl acetate solution was transferred to a constant-pressure dropping funnel and slowly added dropwise to the reaction system over 30 minutes, monitoring the internal temperature to ensure it did not exceed 5°C during the addition. After the addition was complete, the ice-water bath was removed, and the reaction solution was allowed to return to room temperature naturally while stirring for 30 minutes. The reaction flask was then transferred to a preheated oil bath and heated to 80°C with continuous stirring for 16 hours. After the reaction was complete, the oil bath was removed, and the reaction solution was allowed to cool to room temperature. The reaction solution was then slowly poured into a mixture of 100 mL of ice water and 100 mL of saturated sodium bicarbonate aqueous solution for quenching, while stirring. Until no obvious bubbles are generated, the mixture is transferred to a separatory funnel to separate the organic layer. The aqueous phase is extracted with ethyl acetate, and the organic phases are combined and washed successively with deionized water and saturated brine. The separated organic phase is dried with anhydrous sodium sulfate, filtered, and the filter cake is washed with a small amount of ethyl acetate. The filtrates are combined and concentrated under reduced pressure to obtain the crude product. The crude product is purified by silica gel column chromatography, eluted with a mixture of petroleum ether and ethyl acetate, and the fraction containing the target product is collected, concentrated under reduced pressure, and dried in a vacuum drying oven to constant weight to obtain 6.15 g of intermediate.

[0024] ; Under nitrogen protection, 6.15 g of intermediate and 7.75 g of anhydrous potassium carbonate were added to the reaction flask. Then, 100 mL of anhydrous DMF was injected in one go using a syringe. Stirring was started, and the mixture was thoroughly mixed. Next, 5.81 mL of starting material 3 was placed in a constant-pressure dropping funnel and slowly added dropwise to the reaction system over approximately 15 minutes at room temperature. After the addition was complete, the reaction flask was placed in an oil bath at a pre-set temperature and the temperature was slowly raised to 80°C. The reaction was continued at this temperature with stirring for 8 hours. After the reaction was complete, the oil bath was removed, and the mixture was allowed to cool naturally to room temperature. The reaction solution was then poured into 300 mL of ice water and stirred vigorously for 15 minutes. The mixture was quenched and transferred to a separatory funnel. Ethyl acetate was added for extraction, and the organic phase was collected. The aqueous phase was extracted again with ethyl acetate. All organic phases were combined and washed successively with 5% lithium chloride aqueous solution and saturated brine. The separated organic phase was dried with anhydrous sodium sulfate, filtered, and the filter cake was washed with a small amount of ethyl acetate. The filtrates were combined and concentrated under reduced pressure to obtain the crude product. The crude product was separated and purified by silica gel column chromatography. A mixed solution of petroleum ether and ethyl acetate was used for elution. The fraction containing the target product was collected, concentrated under reduced pressure, and dried in a vacuum drying oven to constant weight to obtain 6.99 g of antibacterial agent 1.

[0025] Structural assessment: NMR of antibacterial agent 1: .

[0026] Preparation Examples 2-4 In Preparation Examples 2-4, antibacterial agents 2-4 were prepared sequentially, following the preparation method in Preparation Example 1, except that raw material 1 was replaced, and the rest remained the same as in Preparation Example 1. For details, please refer to Table 1.

[0027] Table 1. Structures and data involved in Preparation Examples 2-4 Example 1

[0028] Preparation of an odor-resistant and high-toughness shoe sole material: 1. Raw material weight parts: Matrix resin (90 parts): is ethylene-vinyl acetate copolymer + thermoplastic elastomer, with a mass ratio of 3:1; Composite deodorant (7.5 parts): It is an antibacterial agent + an adsorbent, with a mass ratio of 1:2. The antibacterial agent is the antibacterial agent 1 prepared in Preparation Example 1, and the adsorbent is bamboo charcoal powder. Toughening agent (15 parts): ethylene-octene copolymer; Filler (30 parts): Silica; Crosslinking agent (3 parts): dicumyl peroxide; Antioxidant (1 part): Antioxidant 1010 + Antioxidant 168, with a mass ratio of 3:1; 2. Preparation method: S1. Pretreatment: Place the adsorbent in a drying oven and dry it at 95℃ for 3 hours until its moisture content is ≤0.5%. After cooling the adsorbent to room temperature, put it into a high-speed mixer, add antibacterial agent, adjust the mixing speed to 1000 r / min, mix for 18 minutes until the material is uniformly mixed to obtain a composite deodorant, which is then sealed for later use. The filler is pulverized to 300 mesh and sieved for later use. S2. Mixing: Put the matrix resin and antioxidant into the internal mixer, adjust the temperature of the internal mixer to 130℃ and the speed to 40r / min, and mix for 6min until the matrix resin is completely melted and mixed evenly with the antioxidant; then add the toughening agent first, stir for 3min and then add the pulverized filler, and continue to mix for 12min to obtain a primary compound with uniform texture. S3. Secondary mixing: Add the prepared composite deodorizing agent and crosslinking agent to the primary mixture, adjust the internal mixer temperature to 140℃ and the speed to 50r / min, and continue mixing for 10min. Through mixing, the composite deodorizing agent and crosslinking agent are fully integrated with the primary mixture, and the components are evenly dispersed to obtain a uniform mixed material. S4. Plasticizing Extrusion: The mixed material is fed into a twin-screw extruder. The temperature of each section of the extruder is controlled as follows: feeding section 120℃, compression section 140℃, homogenization section 150℃, and die head 155℃. The extrusion speed is adjusted to 8m / min. After the material is plasticized and extruded by the extruder, it is cooled and shaped by a water cooling device, and then pelletized by a pelletizer to obtain shoe sole material granules with uniform particle size. S5. Compression molding: After drying the sole material granules, place them into a special mold for soles. Place the mold in a compression molding machine, adjust the compression temperature to 155℃ and the compression pressure to 12MPa, and mold for 10 minutes. Then demold and place the sole semi-finished product in a constant temperature drying oven. Keep it at 70℃ for 2.5 hours to eliminate the internal stress generated during the sole molding process. After cooling to room temperature, an odor-resistant and high-toughness sole material is obtained. Examples 2-4

[0029] The preparation of an odor-resistant and high-toughness shoe sole material is carried out by referring to the preparation method in Example 1, except that the antibacterial agent in the composite odor-resistant agent is replaced with antibacterial agent 2-antibacterial agent 4 prepared in Preparation Examples 2-4, and the rest is the same as in Example 1.

[0030] Comparative Example 1 The preparation of an odor-resistant and high-toughness shoe sole material is carried out according to the preparation method in Example 1, except that the antibacterial agent in the composite odor-resistant agent is not added, and the rest is the same as in Example 1.

[0031] Comparative Example 2 The preparation of an odor-resistant and high-toughness shoe sole material is carried out by referring to the preparation method in Example 1, except that the antibacterial agent in the composite odor-resistant agent is replaced with nano zinc oxide, and the rest is the same as in Example 1.

[0032] Comparative Example 3 The preparation of an odor-resistant and high-toughness shoe sole material is carried out by referring to the preparation method in Example 1, except that the antibacterial agent in the composite odor-resistant agent is replaced with methylisothiazolinone, and the rest is the same as in Example 1.

[0033] Comparative Example 4 The preparation of an odor-resistant and high-toughness shoe sole material is the same as in Example 1, except that no toughening agent is added.

[0034] Performance testing 1. Antibacterial performance test: According to the standard GB / T 38017-2019 "Test method for evaluation of antibacterial performance of footwear and footwear components", common foot odor-causing bacteria Escherichia coli (ATCC 25922) and Staphylococcus aureus (ATCC 6538) were selected. The antibacterial rate of the sole materials prepared in the test examples and comparative examples was calculated as [(number of colonies in blank sample - number of colonies in test sample) / number of colonies in blank sample] × 100%. The results are shown in the table below.

[0035] 2. Odor adsorption performance test: The shoe sole material samples prepared in the examples and comparative examples were placed in a sealed container, and simulated foot odor gas (ammonia) was added. After being kept at a constant temperature of 25°C for 24 hours, the concentration of the remaining odor gas in the container was detected, and the adsorption rate was calculated as [(gas concentration of blank group - gas concentration of sample group) / gas concentration of blank group] × 100%. The results are shown in the table below.

[0036] 3. Tensile strength and elongation at break test: According to standard GB / T 528-2009 "Determination of tensile stress-strain properties of vulcanized rubber or thermoplastic rubber", the tensile strength and elongation at break of the shoe sole materials prepared in the examples and comparative examples were tested, and the results are shown in the table below.

[0037] Table 2. Performance Test Results According to the performance test results in Table 2, this odor-resistant, high-toughness sole material exhibits significant advantages in antibacterial performance, odor adsorption performance, and mechanical properties. Compared with the control group that did not add antibacterial agents or only used traditional antibacterial agents, this invention uses a composite deodorant combining a specific structured antibacterial agent and an adsorbent, achieving a dual improvement in both antibacterial rate and adsorption rate, demonstrating a superior synergistic deodorizing effect. Simultaneously, through the rational addition of toughening agents and the optimization of the cross-linking system, the material maintains high tensile strength while significantly improving elongation at break, effectively solving the problem of insufficient toughness and easy cracking in conventional sole materials, and achieving a good balance between deodorizing performance and mechanical properties.

[0038] Although embodiments of the invention have been shown and described, it will be understood by those skilled in the art that various changes, modifications, substitutions and alterations can be made to these embodiments without departing from the principles and spirit of the invention, the scope of which is defined by the appended claims and their equivalents.

Claims

1. A odor-resistant, high-toughness shoe sole material, characterized in that, By weight, it includes the following components: 80-100 parts of matrix resin, 5-10 parts of composite deodorizer, 10-25 parts of toughening agent, 20-40 parts of filler, 2-5 parts of crosslinking agent, and 0.5-1.5 parts of antioxidant. The composite deodorant is composed of an antibacterial agent and an adsorbent, with a mass ratio of 1:(1-3). The antibacterial agent is a compound shown below: ； Substituents in the compound Selected from: any one of fluorine, hydroxyl, trifluoromethyl, and nitro; The adsorbent is one or more of bamboo charcoal powder, diatomaceous earth, and activated carbon.

2. The odor-resistant, high-toughness shoe sole material according to claim 1, characterized in that, The matrix resin is one or more of ethylene-vinyl acetate copolymer, thermoplastic elastomer, and styrene-butadiene rubber.

3. The odor-resistant, high-toughness shoe sole material according to claim 1, characterized in that, The toughening agent is one or more of ethylene-octene copolymer, polybutadiene rubber, and maleic anhydride-grafted PE.

4. The odor-resistant, high-toughness shoe sole material according to claim 1, characterized in that, The filler is one or more of the following: silica, calcium carbonate, and talc.

5. The odor-resistant, high-toughness shoe sole material according to claim 1, characterized in that, The crosslinking agent is dicumyl peroxide.

6. The odor-resistant, high-toughness shoe sole material according to claim 1, characterized in that, The antioxidant is one or more of antioxidant 1010, antioxidant 168, and antioxidant RD.

7. A method for preparing an odor-resistant, high-toughness shoe sole material according to any one of claims 1-6, characterized in that, Includes the following steps: S1. Pretreatment: Place the adsorbent in the composite deodorant in a drying oven and dry it at 80-105℃ for 2-4 hours to remove moisture from the adsorbent. After cooling to room temperature, mix it evenly with the antibacterial agent to obtain the composite deodorant for later use; pulverize the filler to 200-400 mesh for later use. S2. Mixing: The matrix resin and antioxidant are put into an internal mixer and mixed at 120-140℃ and 30-50r / min for 5-8min until the material is melted and uniform; then the toughening agent and filler are added in sequence, and the mixing is continued for 10-15min to obtain the primary compound. S3. Secondary mixing: Add the prepared composite deodorizing agent and crosslinking agent to the primary mixture, adjust the internal mixer temperature to 130-150℃ and the speed to 40-60r / min, and continue mixing for 8-12min to ensure that each component is evenly dispersed and to obtain a uniform mixed material. S4. Plasticizing extrusion: The compounded material is fed into an extruder, and the temperature of each section of the extruder is controlled as follows: feeding section 110-125℃, compression section 130-145℃, homogenization section 145-155℃, and die head 150-160℃. The extrusion speed is 5-10m / min. After extrusion, the material is cooled, shaped, and granulated to obtain shoe sole material granules. S5. Compression molding: The shoe sole material particles are placed into a shoe sole mold and molded at 150-160℃ and 10-15MPa for 8-12 minutes. Then, the material is demolded and cooled to room temperature to obtain an odor-resistant and high-toughness shoe sole material.

8. The method for preparing an odor-resistant, high-toughness shoe sole material according to claim 7, characterized in that, In step S1, the moisture content of the dried adsorbent is ≤0.5%. When mixing the antibacterial agent and the adsorbent, a high-speed mixer is used with a mixing speed of 800-1200 r / min and a mixing time of 15-20 min.

9. The method for preparing an odor-resistant, high-toughness shoe sole material according to claim 7, characterized in that, In step S2, the feeding sequence of the internal mixer is as follows: first add the matrix resin and antioxidant, then add the toughening agent after melting, and finally add the filler after stirring evenly to avoid filler agglomeration affecting the mixing effect.

10. The method for preparing an odor-resistant, high-toughness shoe sole material according to claim 7, characterized in that, In step S5, the demolded shoe soles need to be placed in a constant temperature drying oven and kept at 60-80℃ for 2-3 hours to eliminate internal stress and further improve the toughness and dimensional stability of the shoe soles.

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