Integrally-formed polymer microcellular foaming slipper material and preparation method thereof

Abstract

The invention relates to the field of slipper materials, in particular to an integrally-formed high-molecular microcellular foaming slipper material and a preparation method thereof, and aims to solve the problems that slippers made of traditional high-molecular microcellular foaming materials are easy to breed bacteria, cause foot infection and generate peculiar smell after being used for a long time due to poor antibacterial performance of the traditional high-molecular microcellular foaming materials; the health and the comfort level of a wearer are influenced; according to the preparation method, through the unique formula design and the synergistic effect of all the components, the material has good softness and elasticity and is more comfortable to wear, a dual antibacterial material is added to serve as a composite modified component, the slipper material has dual antibacterial mechanisms, the antibacterial performance of the slipper material is remarkably improved, and the slipper material is suitable for popularization and application. According to the slipper, the growth of bacteria and fungi can be effectively inhibited, the environment in the slipper is kept clean and sanitary, then the feet of consumers are effectively prevented from being infected by the fungi and the bacteria, and therefore the safe and comfortable use experience is provided for the consumers.

Description

Technical Field

[0001] The present invention relates to the field of slipper materials, and particularly to an integrally formed polymer microcellular foamed slipper material and a preparation method thereof. Background Art

[0002] As a common type of footwear in daily life, the comfort and durability of slippers are the focus of people's attention. Traditional slipper materials often have problems such as excessive hardness and insufficient comfort. With the continuous development of polymer material technology, polymer microcellular foamed materials have been widely used in various slipper products due to their light weight, comfort, good breathability, and good cushioning performance.

[0003] However, the polymer microcellular foamed material has poor antibacterial performance, resulting in the slippers made from it being prone to bacterial growth after long-term use, leading to foot infections and unpleasant odors, which affect the health and comfort of the wearer.

[0004] Therefore, developing an integrally formed polymer microcellular foamed slipper material and a preparation method thereof has important practical significance for improving the antibacterial and bacteriostatic performance of polymer microcellular foamed material slipper products. Summary of the Invention

[0005] In order to overcome the above technical problems, the purpose of the present invention is to provide an integrally formed polymer microcellular foamed slipper material and a preparation method thereof, which solve the problem that the traditional polymer microcellular foamed material has poor antibacterial performance, resulting in the slippers made from it being prone to bacterial growth after long-term use, leading to foot infections and unpleasant odors, which affect the health and comfort of the wearer.

[0006] The purpose of the present invention can be achieved by the following technical solutions: An integrally formed polymer microcellular foamed slipper material, comprising the following components in parts by weight: 35 - 45 parts of ethylene-vinyl acetate copolymer, 0.2 - 2.6 parts of double antibacterial agent, 13 - 17 parts of toughening agent, 6 - 8 parts of flow agent, 3 - 5 parts of anti-shrinkage agent, 5 - 7 parts of talcum powder, 1 - 2 parts of nucleating agent, 1.2 - 1.8 parts of dispersant, 0.6 - 0.7 parts of accelerator, 0.6 - 1.0 parts of cross-linking agent, 2.3 - 2.7 parts of foaming agent, and 5 - 7 parts of titanium dioxide; Among them, the double antibacterial agent is prepared by the following steps: Step a1: Add pentaerythritol, sodium hydroxide, and anhydrous tetrahydrofuran into a three-necked flask equipped with a stirrer, a thermometer, a gas pipe, and a constant-pressure dropping funnel. Introduce nitrogen for protection. Stir and react for 20 - 30 min under the conditions of a temperature of 25 - 30 °C and a stirring rate of 300 - 400 r / min. Then, while stirring, gradually add 3-bromo-1-propene dropwise, controlling the dropping rate at 1 - 2 drops / s. After the addition is complete, raise the temperature to reflux and continue stirring and reacting for 10 - 15 h. After the reaction is completed, cool the reaction product to room temperature, then pour it into anhydrous ether, and then wash it 2 - 3 times with distilled water and saturated brine in sequence. Then dry it with anhydrous sodium sulfate, and then perform vacuum filtration. Rotate and evaporate the filtrate to remove the solvent to obtain a tetra-alkenyl intermediate; Step a2: Add the tetra-alkenyl intermediate, γ-mercaptopropyltrimethoxysilane, and dichloromethane into a three-necked flask equipped with a stirrer, a thermometer, and a gas pipe. Introduce nitrogen for protection. Then stir and react for 40 - 50 min under the conditions of a temperature of 25 - 30 °C and a stirring rate of 300 - 400 r / min. Then raise the temperature to 70 - 75 °C and continue stirring and reacting for 3 - 4 h. After the reaction is completed, cool the reaction product to room temperature, and then rotate and evaporate to remove the solvent to obtain a hyperbranched siloxane; Step a3: Add the hyperbranched siloxane, methyl iodide, silver tetrafluoroborate, and anhydrous acetonitrile into a three-necked flask equipped with a stirrer, a thermometer, and a gas pipe. Introduce nitrogen for protection. Then stir and react for 10 - 20 min under the conditions of a temperature of 25 - 30 °C and a stirring rate of 300 - 400 r / min. Then raise the temperature to 60 - 65 °C and continue stirring and reacting for 8 - 10 h. After the reaction is completed, cool the reaction product to room temperature, then perform vacuum filtration. Rotate and evaporate the filtrate to remove the solvent, and then purify it by column chromatography with a mixed solvent to obtain a hyperbranched sulfonium salt siloxane; Step a4: Add zinc acetate and deionized water into a three-necked flask equipped with a stirrer and a thermometer. Stir and react for 20 - 30 min under the conditions of a temperature of 25 - 30 °C and a stirring rate of 300 - 400 r / min. Then adjust the pH to 10 - 11 with a sodium hydroxide solution. Then raise the temperature to 50 - 55 °C and continue stirring and reacting for 30 - 50 min. Then raise the temperature to 160 - 165 °C and continue stirring and reacting for 10 - 12 h. After the reaction is completed, cool the reaction product to room temperature, then centrifuge. Wash the precipitate 2 - 3 times with distilled water and anhydrous ethanol in sequence, and then place it in a vacuum drying oven and dry it at a temperature of 50 - 55 °C for 3 - 5 h to obtain nano-zinc oxide; Step a5: Add nano-zinc oxide and ethanol solution into a three-necked flask equipped with a stirrer, a thermometer and a gas pipe. Introduce nitrogen for protection, and ultrasonically disperse for 1 - 1.5 h under the condition of an ultrasonic power of 250 - 350 W. Then add hyperbranched sulfonium salt siloxane and continue to ultrasonically disperse for 30 - 40 min. Then stir and react for 20 - 30 min under the conditions of a temperature of 25 - 30 °C and a stirring rate of 300 - 400 r / min. Then raise the temperature to 85 - 90 °C and continue to stir and react for 2 - 3 h. After the reaction is completed, cool the reaction product to room temperature, and then freeze-dry to obtain a double antibacterial material.

[0007] As a further scheme of the present invention: The dosage ratio of the pentaerythritol, sodium hydroxide, anhydrous tetrahydrofuran and 3-bromo-1-propene in step a1 is 10 mmol : 45 - 50 mmol : 40 - 50 mL : 44 - 46 mmol.

[0008] As a further scheme of the present invention: The dosage ratio of the tetraene intermediate, γ-mercaptopropyltrimethoxysilane and dichloromethane in step a2 is 10 mmol : 40 mmol : 60 - 70 mL.

[0009] As a further scheme of the present invention: The dosage ratio of the hyperbranched siloxane, methyl iodide, silver tetrafluoroborate and anhydrous acetonitrile in step a3 is 10 mmol : 44 - 48 mmol : 5 - 6 g : 70 - 80 mL.

[0010] As a further scheme of the present invention: The mixed solvent in step a3 is a mixture of anhydrous methanol and dichloromethane with a volume ratio of 1 : 8 - 10.

[0011] As a further scheme of the present invention: The dosage ratio of zinc acetate and deionized water in step a4 is 5 g : 50 - 60 mL.

[0012] As a further scheme of the present invention: The mass fraction of the sodium hydroxide solution in step a4 is 25 - 35%.

[0013] As a further scheme of the present invention: The dosage ratio of the nano-zinc oxide, ethanol solution and hyperbranched siloxane in step a5 is 5 g : 90 - 100 mL : 0.7 - 4.1 g.

[0014] As a further scheme of the present invention: The volume fraction of the ethanol solution in step a5 is 90 - 95%.

[0015] As a further scheme of the present invention: A preparation method of an integrally formed polymer microporous foaming slipper material, comprising the following steps: Step 1: Weigh 35 - 45 parts by weight of ethylene - vinyl acetate copolymer, 0.2 - 2.6 parts of double antibacterial agent, 13 - 17 parts of toughening agent, 6 - 8 parts of flow agent, 3 - 5 parts of anti - shrinkage agent, 5 - 7 parts of talcum powder, 1 - 2 parts of nucleating agent, 1.2 - 1.8 parts of dispersant, 0.6 - 0.7 parts of accelerator, 0.6 - 1.0 parts of cross - linking agent, 2.3 - 2.7 parts of foaming agent and 5 - 7 parts of titanium dioxide, and set aside; Step 2: Add the ethylene - vinyl acetate copolymer, double antibacterial agent, toughening agent, flow agent, anti - shrinkage agent, talcum powder, nucleating agent, dispersant, accelerator, cross - linking agent, foaming agent and titanium dioxide into a high - speed mixer, and stir and mix at a temperature of 25 - 30 °C and a stirring rate of 800 - 1200 r / min for 10 - 20 min to obtain a premix; Step 3: Add the premix into a twin - screw extruder, and melt - extrude at a temperature of 150 - 180 °C and a screw speed of 150 - 200 r / min, and then granulate to obtain an integrally formed high - molecular microporous foaming slipper material.

[0016] As a further scheme of the present invention: The ethylene - vinyl acetate copolymer is Formosa Plastics eva7470m.

[0017] As a further scheme of the present invention: The toughening agent is POE - LC168 toughening agent.

[0018] As a further scheme of the present invention: The flow agent is HZ - 303PP flow agent.

[0019] As a further scheme of the present invention: The anti - shrinkage agent is JQ9107 anti - shrinkage agent.

[0020] As a further scheme of the present invention: The nucleating agent is magnesium oxide.

[0021] As a further scheme of the present invention: The dispersant is zinc stearate.

[0022] As a further scheme of the present invention: The accelerator is stearic acid.

[0023] As a further scheme of the present invention: The cross - linking agent is BIBP cross - linking agent.

[0024] As a further scheme of the present invention: The foaming agent is AC foaming agent.

[0025] The beneficial effects of the present invention: An integrally formed polymer microcellular foaming slipper material and a preparation method thereof according to the present invention. By adding ethylene-vinyl acetate copolymer, double antibacterial agent, toughening agent, flow agent, anti-shrinkage agent, talcum powder, nucleating agent, dispersant, accelerator, bridging agent, foaming agent and titanium dioxide into a high-speed mixer and stirring and mixing, a premix is obtained. The premix is added to a twin-screw extruder for melt extrusion and granulated to obtain an integrally formed polymer microcellular foaming slipper material. Through unique formulation design, each component acts synergistically, making the material have good softness and elasticity, more comfortable to wear. And a double antibacterial agent is added as a composite modification component, enabling the slipper material to have a double antibacterial mechanism, significantly improving the antibacterial performance of the slipper material, effectively inhibiting the growth of bacteria and fungi, maintaining the cleanliness of the internal environment of the slipper, and thus effectively preventing fungal and bacterial infections of consumers' feet, thereby providing consumers with a safe and comfortable use experience.

[0026] In the process of preparing the polymer microcellular foaming slipper material, a double antibacterial agent was first prepared. Using pentaerythritol and 3-bromo-1-propene to react, the hydroxyl group on pentaerythritol reacts with the bromine atom on 3-bromo-1-propene to form a tetra-alkenyl-containing tetra-alkenyl intermediate. Then the tetra-alkenyl intermediate reacts with γ-mercaptopropyltrimethoxysilane, and the alkenyl group on the tetra-alkenyl intermediate reacts with the mercapto group on γ-mercaptopropyltrimethoxysilane through click chemical reaction to form four thioether structures and introduce a large number of siloxane groups to obtain hyperbranched siloxane. Then hyperbranched siloxane reacts with methyl iodide, and the thioether structure on hyperbranched siloxane reacts with iodine atoms to form a sulfonium salt structure to obtain hyperbranched sulfonium salt siloxane. Then nano-zinc oxide is prepared using zinc acetate as a raw material, and then hyperbranched sulfonium salt siloxane is used to modify nano-zinc oxide. The siloxane on hyperbranched sulfonium salt siloxane hydrolyzes to form silanol and grafts onto the surface of nano-zinc oxide particles, thereby wrapping nano-zinc oxide to obtain a double antibacterial agent. The nano-zinc oxide in this double antibacterial agent can release zinc ions, and the zinc ions can combine with the negative charges on the bacterial cell membrane to destroy the integrity of the cell membrane. In addition, nano-zinc oxide can also generate reactive oxygen species, and these reactive oxygen species can oxidize biological macromolecules in bacterial cells, thus achieving an antibacterial effect. The hyperbranched sulfonium salt siloxane in this double antibacterial agent provides a large number of sulfonium cations. When the sulfonium cations come into contact with bacteria, they will adsorb onto the bacterial cell membrane and then destroy the integrity of the cell membrane, thereby achieving an antibacterial effect. Through the grafting and coating effect of hyperbranched sulfonium salt siloxane, a coating layer is formed, and this coating layer can effectively prevent the aggregation of nano-zinc oxide particles, enabling nano-zinc oxide to be evenly dispersed in the polymer matrix, effectively improving the dispersibility and stability of nano-zinc oxide in the polymer matrix, and the synergistic effect of multiple antibacterial and bacteriostatic actions can make it difficult for bacteria to develop drug resistance, significantly enhancing the antibacterial and bacteriostatic effect and durability of the double antibacterial agent. Detailed implementation mode

[0027] Next, in combination with the embodiments of the present invention, the technical solutions in the embodiments of the present invention will be clearly and completely described. Obviously, the described embodiments are only a part of the embodiments of the present invention, rather than all the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without making creative efforts belong to the protection scope of the present invention.

[0028] Embodiment 1: This embodiment is a preparation method of an integrally formed polymer microporous foaming slipper material, including the following steps: Step S1: Add 10 mmol of pentaerythritol, 45 mmol of sodium hydroxide, and 40 mL of anhydrous tetrahydrofuran into a three-necked flask equipped with a stirrer, a thermometer, a gas pipe, and a constant pressure dropping funnel, introduce nitrogen protection, stir and react for 20 min under the conditions of a temperature of 25 °C and a stirring rate of 300 r / min. Then, while stirring, gradually dropwise add 44 mmol of 3-bromo-1-propene, control the dropping rate at 1 drop / s. After the dropping is completed, continue to stir and react for 10 h under reflux conditions. After the reaction is completed, cool the reaction product to room temperature, then pour it into anhydrous ether, and then wash it twice with distilled water and saturated brine respectively. Then dry it with anhydrous sodium sulfate, and then perform vacuum filtration. Rotate and evaporate the filtrate to remove the solvent to obtain a tetraene intermediate; Step S2: Add 10 mmol of tetraene intermediate, 40 mmol of γ-mercaptopropyltrimethoxysilane, and 60 mL of dichloromethane into a three-necked flask equipped with a stirrer, a thermometer, and a gas pipe, introduce nitrogen protection, and then stir and react for 40 min under the conditions of a temperature of 25 °C and a stirring rate of 300 r / min. Then continue to stir and react for 3 h under the condition of heating to 70 °C. After the reaction is completed, cool the reaction product to room temperature, and then rotate and evaporate to remove the solvent to obtain a hyperbranched siloxane; Step S3: Add 10 mmol of hyperbranched siloxane, 44 mmol of methyl iodide, 5 g of silver tetrafluoroborate, and 70 mL of anhydrous acetonitrile into a three-necked flask equipped with a stirrer, a thermometer, and a gas pipe, introduce nitrogen protection, and then stir and react for 10 min under the conditions of a temperature of 25 °C and a stirring rate of 300 r / min. Then continue to stir and react for 8 h under the condition of heating to 60 °C. After the reaction is completed, cool the reaction product to room temperature, then perform vacuum filtration, rotate and evaporate the filtrate to remove the solvent, and then perform column chromatography purification with a mixed solvent composed of anhydrous methanol and dichloromethane in a volume ratio of 1:8 to obtain a hyperbranched sulfonium salt siloxane; Step S4: Add 5 g of zinc acetate and 50 mL of deionized water into a three-necked flask equipped with a stirrer and a thermometer. Stir and react for 20 min at a temperature of 25°C and a stirring rate of 300 r / min. Then adjust the pH to 10 with a 25% sodium hydroxide solution. Then continue to stir and react for 30 min at a temperature of 50°C, and then continue to stir and react for 10 h at a temperature of 160°C. After the reaction is completed, cool the reaction product to room temperature, then centrifuge, wash the precipitate with distilled water and absolute ethanol twice respectively, and then place it in a vacuum drying oven and dry for 3 h at a temperature of 50°C to obtain nano-zinc oxide; Step S5: Add 5 g of nano-zinc oxide and 90 mL of ethanol solution with a volume fraction of 90% into a three-necked flask equipped with a stirrer, a thermometer and a gas guide tube. Pass in nitrogen for protection and ultrasonically disperse for 1 h under the condition of an ultrasonic power of 250 W. Then add 0.7 g of hyperbranched sulfonium salt siloxane and continue to ultrasonically disperse for 30 min. Then stir and react for 20 min at a temperature of 25°C and a stirring rate of 300 r / min. Then continue to stir and react for 2 h at a temperature of 85°C. After the reaction is completed, cool the reaction product to room temperature, and then freeze-dry to obtain a double antibacterial material; Step S6: Weigh 35 parts of ethylene-vinyl acetate copolymer, 0.2 part of double antibacterial material, 13 parts of toughening agent, 6 parts of flow agent, 3 parts of anti-shrinkage agent, 5 parts of talcum powder, 1 part of nucleating agent, 1.2 parts of dispersant, 0.6 part of accelerator, 0.6 part of cross-linking agent, 2.3 parts of foaming agent and 5 parts of titanium dioxide according to weight, and set aside; the ethylene-vinyl acetate copolymer is Taifu eva7470m; the toughening agent is POE-LC168 toughening agent; the flow agent is HZ-303PP flow agent; the anti-shrinkage agent is JQ9107 anti-shrinkage agent; the nucleating agent is magnesium oxide; the dispersant is zinc stearate; the accelerator is stearic acid; the cross-linking agent is BIBP cross-linking agent; the foaming agent is AC foaming agent; Step S7: Add the ethylene-vinyl acetate copolymer, double antibacterial material, toughening agent, flow agent, anti-shrinkage agent, talcum powder, nucleating agent, dispersant, accelerator, cross-linking agent, foaming agent and titanium dioxide into a high-speed mixer and stir and mix for 10 min at a temperature of 25°C and a stirring rate of 800 r / min to obtain a premix; Step S8: Add the premix into a twin-screw extruder and melt-extrude at a temperature of 150°C and a screw speed of 150 r / min, and then granulate to obtain an integrally formed polymer microporous foamed slipper material.

[0029] Example 2: This example is a preparation method of an integrally formed polymer microporous foamed slipper material, including the following steps: Step S1: Add 10 mmol of pentaerythritol, 48 mmol of sodium hydroxide, and 45 mL of anhydrous tetrahydrofuran into a three-necked flask equipped with a stirrer, a thermometer, a gas pipe, and a constant-pressure dropping funnel. Introduce nitrogen for protection. Stir and react for 25 min under the conditions of a temperature of 28 °C and a stirring rate of 350 r / min. Then, while stirring, gradually add dropwise 45 mmol of 3-bromo-1-propene, controlling the dropping rate at 1 drop / s. After the addition is complete, raise the temperature to reflux and continue stirring and reacting for 12 h. After the reaction is completed, cool the reaction product to room temperature, then pour it into anhydrous ether, and then wash it twice with distilled water and saturated brine in sequence. Then dry it with anhydrous sodium sulfate, and then perform vacuum filtration. Rotate and evaporate the filtrate to remove the solvent to obtain a tetra-alkenyl intermediate; Step S2: Add 10 mmol of the tetra-alkenyl intermediate, 40 mmol of γ-mercaptopropyltrimethoxysilane, and 65 mL of dichloromethane into a three-necked flask equipped with a stirrer, a thermometer, and a gas pipe. Introduce nitrogen for protection. Then stir and react for 45 min under the conditions of a temperature of 28 °C and a stirring rate of 350 r / min. Then raise the temperature to 72 °C and continue stirring and reacting for 3.5 h. After the reaction is completed, cool the reaction product to room temperature, and then rotate and evaporate to remove the solvent to obtain a hyperbranched siloxane; Step S3: Add 10 mmol of the hyperbranched siloxane, 46 mmol of methyl iodide, 5.5 g of silver tetrafluoroborate, and 75 mL of anhydrous acetonitrile into a three-necked flask equipped with a stirrer, a thermometer, and a gas pipe. Introduce nitrogen for protection. Then stir and react for 15 min under the conditions of a temperature of 28 °C and a stirring rate of 350 r / min. Then raise the temperature to 62 °C and continue stirring and reacting for 9 h. After the reaction is completed, cool the reaction product to room temperature, then perform vacuum filtration. Rotate and evaporate the filtrate to remove the solvent, and then perform column chromatography purification with a mixed solvent composed of anhydrous methanol and dichloromethane in a volume ratio of 1:9 to obtain a hyperbranched sulfonium salt siloxane; Step S4: Add 5 g of zinc acetate and 55 mL of deionized water into a three-necked flask equipped with a stirrer and a thermometer. Stir and react for 25 min under the conditions of a temperature of 28 °C and a stirring rate of 350 r / min. Then adjust the pH to 10.5 with a 30% sodium hydroxide solution by mass fraction. Then raise the temperature to 52 °C and continue stirring and reacting for 40 min. Then raise the temperature to 162 °C and continue stirring and reacting for 11 h. After the reaction is completed, cool the reaction product to room temperature, then centrifuge. Wash the precipitate twice with distilled water and anhydrous ethanol in sequence. Then place it in a vacuum drying oven and dry it at a temperature of 52 °C for 4 h to obtain nano-zinc oxide; Step S5: Add 5 g of nano-zinc oxide and 95 mL of ethanol solution with a volume fraction of 92% into a three-necked flask equipped with a stirrer, a thermometer, and a gas guide tube. Protect it by introducing nitrogen. Under the condition of an ultrasonic power of 300 W, ultrasonically disperse for 1 h. Then add 2.4 g of hyperbranched sulfonium salt siloxane and continue ultrasonically dispersing for 35 min. Then, under the conditions of a temperature of 28 °C and a stirring rate of 350 r / min, stir and react for 25 min. Then raise the temperature to 88 °C and continue stirring and reacting for 2.5 h. After the reaction is completed, cool the reaction product to room temperature, and then freeze-dry to obtain a double antibacterial material; Step S6: Weigh 40 parts of ethylene-vinyl acetate copolymer, 1.4 parts of double antibacterial material, 15 parts of toughening agent, 7 parts of flow agent, 4 parts of anti-shrinkage agent, 6 parts of talcum powder, 1.5 parts of nucleating agent, 1.5 parts of dispersant, 0.65 parts of accelerator, 0.8 parts of cross-linking agent, 2.5 parts of foaming agent, and 6 parts of titanium dioxide according to parts by weight for standby; the ethylene-vinyl acetate copolymer is Taifu eva7470m; the toughening agent is POE-LC168 toughening agent; the flow agent is HZ-303PP flow agent; the anti-shrinkage agent is JQ9107 anti-shrinkage agent; the nucleating agent is magnesium oxide; the dispersant is zinc stearate; the accelerator is stearic acid; the cross-linking agent is BIBP cross-linking agent; the foaming agent is AC foaming agent; Step S7: Add the ethylene-vinyl acetate copolymer, double antibacterial material, toughening agent, flow agent, anti-shrinkage agent, talcum powder, nucleating agent, dispersant, accelerator, cross-linking agent, foaming agent, and titanium dioxide into a high-speed mixer, and stir and mix at a temperature of 28 °C and a stirring rate of 1000 r / min for 15 min to obtain a premix; Step S8: Add the premix into a twin-screw extruder and melt-extrude at a temperature of 165 °C and a screw speed of 175 r / min, and then granulate to obtain an integrally formed high-molecular microporous foamed slipper material.

[0030] Example 3: This example is a preparation method of an integrally formed high-molecular microporous foamed slipper material, including the following steps: Step S1: Add 10 mmol of pentaerythritol, 50 mmol of sodium hydroxide, and 50 mL of anhydrous tetrahydrofuran into a three-necked flask equipped with a stirrer, a thermometer, a gas pipe, and a constant-pressure dropping funnel. Introduce nitrogen for protection. Stir and react for 30 min under the conditions of a temperature of 30 °C and a stirring rate of 400 r / min. Then, while stirring, gradually add 46 mmol of 3-bromo-1-propene dropwise, controlling the dropping rate at 2 drops / s. After the addition is complete, raise the temperature to reflux and continue stirring and reacting for 15 h. After the reaction is completed, cool the reaction product to room temperature, then pour it into anhydrous ether, and then wash it 3 times with distilled water and saturated brine in sequence. Then dry it with anhydrous sodium sulfate, and then perform vacuum filtration. Rotate and evaporate the filtrate to remove the solvent to obtain a tetra-alkenyl intermediate; Step S2: Add 10 mmol of the tetra-alkenyl intermediate, 40 mmol of γ-mercaptopropyltrimethoxysilane, and 70 mL of dichloromethane into a three-necked flask equipped with a stirrer, a thermometer, and a gas pipe. Introduce nitrogen for protection. Then stir and react for 50 min under the conditions of a temperature of 30 °C and a stirring rate of 400 r / min. Then raise the temperature to 75 °C and continue stirring and reacting for 4 h. After the reaction is completed, cool the reaction product to room temperature, and then rotate and evaporate to remove the solvent to obtain a hyperbranched siloxane; Step S3: Add 10 mmol of the hyperbranched siloxane, 48 mmol of methyl iodide, 6 g of silver tetrafluoroborate, and 80 mL of anhydrous acetonitrile into a three-necked flask equipped with a stirrer, a thermometer, and a gas pipe. Introduce nitrogen for protection. Then stir and react for 20 min under the conditions of a temperature of 30 °C and a stirring rate of 400 r / min. Then raise the temperature to 65 °C and continue stirring and reacting for 10 h. After the reaction is completed, cool the reaction product to room temperature, and then perform vacuum filtration. Rotate and evaporate the filtrate to remove the solvent, and then purify it by column chromatography with a mixed solvent composed of anhydrous methanol and dichloromethane in a volume ratio of 1:10 to obtain a hyperbranched sulfonium salt siloxane; Step S4: Add 5 g of zinc acetate and 60 mL of deionized water into a three-necked flask equipped with a stirrer and a thermometer. Stir and react for 30 min under the conditions of a temperature of 30 °C and a stirring rate of 400 r / min. Then adjust the pH to 11 with a 35% sodium hydroxide solution by mass fraction. Then raise the temperature to 55 °C and continue stirring and reacting for 50 min. Then raise the temperature to 165 °C and continue stirring and reacting for 12 h. After the reaction is completed, cool the reaction product to room temperature, and then centrifuge. Wash the precipitate 3 times with distilled water and anhydrous ethanol in sequence. Then place it in a vacuum drying oven and dry it at a temperature of 55 °C for 5 h to obtain nano-zinc oxide; Step S5: Add 5 g of nano-zinc oxide and 100 mL of ethanol solution with a volume fraction of 95% into a three-necked flask equipped with a stirrer, a thermometer and a gas pipe. Protect with nitrogen. Under the condition of an ultrasonic power of 350 W, ultrasonically disperse for 1.5 h. Then add 4.1 g of hyperbranched sulfonium salt siloxane and continue to ultrasonically disperse for 40 min. Then stir and react for 30 min under the conditions of a temperature of 30 °C and a stirring rate of 400 r / min. Then raise the temperature to 90 °C and continue to stir and react for 3 h. After the reaction is completed, cool the reaction product to room temperature, and then freeze-dry to obtain a double antibacterial material; Step S6: Weigh 45 parts of ethylene-vinyl acetate copolymer, 2.6 parts of double antibacterial material, 17 parts of toughening agent, 8 parts of flow agent, 5 parts of anti-shrinkage agent, 7 parts of talc powder, 2 parts of nucleating agent, 1.8 parts of dispersant, 0.7 parts of accelerator, 1.0 part of cross-linking agent, 2.7 parts of foaming agent and 7 parts of titanium dioxide according to parts by weight for standby; the ethylene-vinyl acetate copolymer is Taifu eva7470m; the toughening agent is POE-LC168 toughening agent; the flow agent is HZ-303PP flow agent; the anti-shrinkage agent is JQ9107 anti-shrinkage agent; the nucleating agent is magnesium oxide; the dispersant is zinc stearate; the accelerator is stearic acid; the cross-linking agent is BIBP cross-linking agent; the foaming agent is AC foaming agent; Step S7: Add the ethylene-vinyl acetate copolymer, double antibacterial material, toughening agent, flow agent, anti-shrinkage agent, talc powder, nucleating agent, dispersant, accelerator, cross-linking agent, foaming agent and titanium dioxide into a high-speed mixer, and stir and mix at a temperature of 30 °C and a stirring rate of 1200 r / min for 20 min to obtain a premix; Step S8: Add the premix into a twin-screw extruder, and melt and extrude at a temperature of 180 °C and a screw speed of 200 r / min, and granulate to obtain an integrally formed polymer microporous foamed slipper material.

[0031] Comparative Example 1: This comparative example is a preparation method of an integrally formed polymer microporous foamed slipper material, including the following steps: Step S1: Weigh 45 parts by weight of ethylene-vinyl acetate copolymer, 17 parts of toughening agent, 8 parts of flow agent, 5 parts of anti-shrinkage agent, 7 parts of talcum powder, 2 parts of nucleating agent, 1.8 parts of dispersant, 0.7 part of accelerator, 1.0 part of cross-linking agent, 2.7 parts of foaming agent and 7 parts of titanium dioxide for standby; the ethylene-vinyl acetate copolymer is Formosa Plastics eva7470m; the toughening agent is POE-LC168 toughening agent; the flow agent is HZ-303PP flow agent; the anti-shrinkage agent is JQ9107 anti-shrinkage agent; the nucleating agent is magnesium oxide; the dispersant is zinc stearate; the accelerator is stearic acid; the cross-linking agent is BIBP cross-linking agent; the foaming agent is AC foaming agent; Step S2: Add the ethylene-vinyl acetate copolymer, toughening agent, flow agent, anti-shrinkage agent, talcum powder, nucleating agent, dispersant, accelerator, cross-linking agent, foaming agent and titanium dioxide into a high-speed mixer, and stir and mix for 20 min under the conditions of a temperature of 30°C and a stirring rate of 1200 r / min to obtain a premix; Step S3: Add the premix into a twin-screw extruder, and melt and extrude under the conditions of a temperature of 180°C and a screw speed of 200 r / min, and granulate to obtain an integrally formed high-molecular microporous foaming slipper material.

[0032] Comparative Example 2: This comparative example is a preparation method of an integrally formed high-molecular microporous foaming slipper material, including the following steps: Step S1: Add 10 mmol of pentaerythritol, 50 mmol of sodium hydroxide, and 50 mL of anhydrous tetrahydrofuran into a three-necked flask equipped with a stirrer, a thermometer, a gas guide tube, and a constant pressure dropping funnel, introduce nitrogen protection, and stir and react for 30 min under the conditions of a temperature of 30°C and a stirring rate of 400 r / min. Then, while stirring, gradually dropwise add 46 mmol of 3-bromo-1-propene, control the dropping rate to be 2 drops / s. After the dropping is completed, raise the temperature to reflux and continue to stir and react for 15 h. After the reaction is completed, cool the reaction product to room temperature, then pour it into anhydrous ether, and then wash it 3 times with distilled water and saturated brine in sequence. Then dry it with anhydrous sodium sulfate, and then perform vacuum filtration. Rotate and evaporate the filtrate to remove the solvent to obtain a tetra-alkenyl intermediate; Step S2: Add 10 mmol of tetra-alkenyl intermediate, 40 mmol of γ-mercaptopropyltrimethoxysilane, and 70 mL of dichloromethane into a three-necked flask equipped with a stirrer, a thermometer, and a gas guide tube, introduce nitrogen protection, and then stir and react for 50 min under the conditions of a temperature of 30°C and a stirring rate of 400 r / min. Then raise the temperature to 75°C and continue to stir and react for 4 h. After the reaction is completed, cool the reaction product to room temperature, and then rotate and evaporate to remove the solvent to obtain a hyperbranched siloxane; Step S3: Add 10 mmol of hyperbranched siloxane, 48 mmol of methyl iodide, 6 g of silver tetrafluoroborate, and 80 mL of anhydrous acetonitrile into a three-necked flask equipped with a stirrer, a thermometer, and a gas pipe. Introduce nitrogen for protection. Then, stir and react for 20 min under the conditions of a temperature of 30 °C and a stirring rate of 400 r / min. After that, continue to stir and react for 10 h under the condition of raising the temperature to 65 °C. After the reaction is completed, cool the reaction product to room temperature, then perform vacuum filtration. Rotate and evaporate the filtrate to remove the solvent. Then, carry out column chromatography purification with a mixed solvent composed of anhydrous methanol and dichloromethane in a volume ratio of 1:10 to obtain hyperbranched sulfonium salt siloxane; Step S4: Weigh 45 parts by weight of ethylene-vinyl acetate copolymer, 2.6 parts of hyperbranched sulfonium salt siloxane, 17 parts of toughening agent, 8 parts of flow agent, 5 parts of anti-shrinkage agent, 7 parts of talc powder, 2 parts of nucleating agent, 1.8 parts of dispersant, 0.7 part of accelerator, 1.0 part of cross-linking agent, 2.7 parts of foaming agent, and 7 parts of titanium dioxide, and set aside; The ethylene-vinyl acetate copolymer is Taifu eva7470m; The toughening agent is POE-LC168 toughening agent; The flow agent is HZ-303PP flow agent; The anti-shrinkage agent is JQ9107 anti-shrinkage agent; The nucleating agent is magnesium oxide; The dispersant is zinc stearate; The accelerator is stearic acid; The cross-linking agent is BIBP cross-linking agent; The foaming agent is AC foaming agent; Step S5: Add the ethylene-vinyl acetate copolymer, hyperbranched sulfonium salt siloxane, toughening agent, flow agent, anti-shrinkage agent, talc powder, nucleating agent, dispersant, accelerator, cross-linking agent, foaming agent, and titanium dioxide into a high-speed mixer, and stir and mix for 20 min under the conditions of a temperature of 30 °C and a stirring rate of 1200 r / min to obtain a premix; Step S6: Add the premix into a twin-screw extruder, and melt and extrude under the conditions of a temperature of 180 °C and a screw speed of 200 r / min, and then granulate to obtain an integrally formed polymer microporous foaming slipper material.

[0033] Comparative Example 3: This comparative example is a preparation method of an integrally formed polymer microporous foaming slipper material, including the following steps: Step S1: Add 5 g of zinc acetate and 60 mL of deionized water into a three-necked flask equipped with a stirrer and a thermometer. Stir and react for 30 min under the conditions of a temperature of 30 °C and a stirring rate of 400 r / min. Then, adjust the pH to 11 with a 35% sodium hydroxide solution. After that, continue to stir and react for 50 min under the condition of heating to 55 °C, and then continue to stir and react for 12 h under the condition of heating to 165 °C. After the reaction is completed, cool the reaction product to room temperature, then centrifuge, wash the precipitate with distilled water and absolute ethanol three times each, and then place it in a vacuum drying oven and dry it at a temperature of 55 °C for 5 h to obtain nano-zinc oxide; Step S2: Weigh 45 parts by weight of ethylene-vinyl acetate copolymer, 2.6 parts of nano-zinc oxide, 17 parts of toughening agent, 8 parts of flow agent, 5 parts of anti-shrinkage agent, 7 parts of talcum powder, 2 parts of nucleating agent, 1.8 parts of dispersant, 0.7 part of accelerator, 1.0 part of cross-linking agent, 2.7 parts of foaming agent and 7 parts of titanium dioxide, and set aside; the ethylene-vinyl acetate copolymer is Formosa Plastics eva7470m; the toughening agent is POE-LC168 toughening agent; the flow agent is HZ-303PP flow agent; the anti-shrinkage agent is JQ9107 anti-shrinkage agent; the nucleating agent is magnesium oxide; the dispersant is zinc stearate; the accelerator is stearic acid; the cross-linking agent is BIBP cross-linking agent; the foaming agent is AC foaming agent; Step S3: Add the ethylene-vinyl acetate copolymer, nano-zinc oxide, toughening agent, flow agent, anti-shrinkage agent, talcum powder, nucleating agent, dispersant, accelerator, cross-linking agent, foaming agent and titanium dioxide into a high-speed mixer, and stir and mix for 20 min under the conditions of a temperature of 30 °C and a stirring rate of 1200 r / min to obtain a premix; Step S4: Add the premix into a twin-screw extruder, and melt and extrude it under the conditions of a temperature of 180 °C and a screw speed of 200 r / min, and then granulate to obtain an integrally formed polymer microporous foamed slipper material.

[0034] Comparative Example 4: This comparative example is a preparation method of an integrally formed polymer microporous foamed slipper material, which includes the following steps: Step S1: Weigh 45 parts of ethylene-vinyl acetate copolymer, 1.3 parts of octyldecyldimethylammonium chloride, 1.3 parts of nano-zinc oxide, 17 parts of toughening agent, 8 parts of flow agent, 5 parts of anti-shrinkage agent, 7 parts of talcum powder, 2 parts of nucleating agent, 1.8 parts of dispersant, 0.7 parts of accelerator, 1.0 part of cross-linking agent, 2.7 parts of foaming agent and 7 parts of titanium dioxide for standby; the ethylene-vinyl acetate copolymer is Formosa Plastics eva7470m; the toughening agent is POE-LC168 toughening agent; the flow agent is HZ-303PP flow agent; the anti-shrinkage agent is JQ9107 anti-shrinkage agent; the nucleating agent is magnesium oxide; the dispersant is zinc stearate; the accelerator is stearic acid; the cross-linking agent is BIBP cross-linking agent; the foaming agent is AC foaming agent; Step S2: Add the ethylene-vinyl acetate copolymer, octyldecyldimethylammonium chloride, nano-zinc oxide, toughening agent, flow agent, anti-shrinkage agent, talcum powder, nucleating agent, dispersant, accelerator, cross-linking agent, foaming agent and titanium dioxide into a high-speed mixer, and stir and mix at a temperature of 30°C and a stirring rate of 1200 r / min for 20 min to obtain a premix; Step S3: Add the premix to a twin-screw extruder, and melt and extrude at a temperature of 180°C and a screw speed of 200 r / min, and granulate to obtain an integrally formed high molecular microporous foamed slipper material.

[0035] Inject the integrally formed high molecular microporous foamed slipper materials of Examples 1-3 and Comparative Examples 1-4 into a slipper style mold, foam and shape at a temperature of 180°C and a pressure of 10 MPa for 5 min, then release the pressure and cool. Then, use Staphylococcus aureus, Candida albicans and Escherichia coli as experimental strains, and according to QB / T 2591-2003 "Test Methods and Antibacterial Effects of Antibacterial Plastics", detect the antibacterial and bacteriostatic properties of the formed integrally formed foamed slippers. The test results are shown in the following table:

[0036] Referring to the data in the above table, according to the comparison between Examples 1-3 and Comparative Examples 1-4, it can be known that the high molecular microporous foamed slipper material of the present application has excellent antibacterial and bacteriostatic properties.

[0037] In the description of this specification, the description referring to terms such as "one embodiment", "example", "specific example", etc. 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 invention. In this specification, the schematic representations of the above terms do not necessarily refer to the same embodiment or example. Moreover, the specific features, structures, materials or characteristics described can be combined in a suitable manner in any one or more embodiments or examples.

[0038] The above content is only an example and explanation of the present invention. Those skilled in the art of the present technology can make various modifications, supplements, or use similar methods for substitution to the specific embodiments described. As long as they do not deviate from the invention or exceed the scope defined by this application, they should all fall within the protection scope of the present invention.

Claims

1. An integrally formed polymer microporous foam slipper material, characterized in that: It includes the following components by weight: 35-45 parts of ethylene-vinyl acetate copolymer, 0.2-2.6 parts of dual antibacterial material, 13-17 parts of toughening agent, 6-8 parts of flow agent, 3-5 parts of anti-shrinkage agent, 5-7 parts of talc, 1-2 parts of nucleating agent, 1.2-1.8 parts of dispersant, 0.6-0.7 parts of accelerator, 0.6-1.0 parts of bridging agent, 2.3-2.7 parts of foaming agent and 5-7 parts of titanium dioxide; Wherein, the dual antibacterial material is prepared by the following steps: Step a1: stirring pentaerythritol, sodium hydroxide and anhydrous tetrahydrofuran for reaction, then adding 3-bromo-1-propylene dropwise while stirring, and continuing to stir the reaction after the addition is complete. After the reaction is complete, the reaction product is cooled, then poured into anhydrous ether, then washed and dried, and then vacuum filtered, and the filtrate is rotary evaporated to obtain a tetraenyl intermediate; Step a2: stirring the tetraenyl intermediate, γ-mercaptopropyltrimethoxysilane and dichloromethane for reaction, cooling the reaction product after the reaction is completed, and then rotary evaporating to obtain hyperbranched siloxane; Step a3: stirring a hyperbranched siloxane, methyl iodide, silver tetrafluoroborate and anhydrous acetonitrile to react, cooling the reaction product after the reaction is completed, then vacuum filtering, rotary evaporating the filtrate, and then purifying it by column chromatography with a mixed solvent to obtain a hyperbranched sulfonium salt siloxane; Step a4: stirring zinc acetate and deionized water for reaction, then adjusting the pH with sodium hydroxide solution, and then continuing to stir the reaction. After the reaction is completed, the reaction product is cooled, then centrifuged, and the precipitate is washed and dried to obtain nano zinc oxide; Step a5: Ultrasonic dispersion of nano zinc oxide and ethanol solution, then adding hyperbranched sulfonium salt siloxane and continuing ultrasonic dispersion, followed by stirring reaction, cooling the reaction product after the reaction is completed, and then freeze-drying to obtain a dual antibacterial material.

2. The one-piece polymer microporous foamed slipper material according to claim 1, characterized in that: The usage ratio of the pentaerythritol, sodium hydroxide, anhydrous tetrahydrofuran and 3-bromo-1-propylene in step a1 is 10 mmol: 45-50 mmol: 40-50 mL: 44-46 mmol.

3. The one-piece polymer microporous foamed slipper material according to claim 1, characterized in that: The usage ratio of the tetraenyl intermediate, γ-mercaptopropyltrimethoxysilane and dichloromethane in step a2 is 10 mmol:40 mmol:60-70 mL.

4. The one-piece polymer microporous foamed slipper material according to claim 1, characterized in that: The hyperbranched siloxane, iodomethane, silver tetrafluoroborate and anhydrous acetonitrile in step a3 are used in a ratio of 10 mmol:44-48 mmol:5-6 g:70-80 mL; the mixed solvent is a mixture of anhydrous methanol and dichloromethane in a volume ratio of 1:8-10.

5. The one-piece polymer microporous foamed slipper material according to claim 1, characterized in that: The dosage ratio of the zinc acetate and deionized water in step a4 is 5g:50-60mL.

6. The one-piece polymer microporous foamed slipper material according to claim 1, characterized in that: The mass fraction of the sodium hydroxide solution in step a4 is 25-35%.

7. The one-piece polymer microporous foamed slipper material according to claim 1, characterized in that: The usage ratio of the nano zinc oxide, ethanol solution and hyperbranched siloxane in step a5 is 5g:90-100mL:0.7-4.1g.

8. The one-piece polymer microporous foamed slipper material according to claim 1, characterized in that: The volume fraction of the ethanol solution in step a5 is 90-95%.

9. A method for preparing the integrally formed polymer microporous foamed slipper material according to any one of claims 1 to 8, characterized in that: The following steps are involved: Step 1: Weigh 35-45 parts of ethylene-vinyl acetate copolymer, 0.2-2.6 parts of dual antibacterial material, 13-17 parts of toughening agent, 6-8 parts of flow agent, 3-5 parts of anti-shrinkage agent, 5-7 parts of talc, 1-2 parts of nucleating agent, 1.2-1.8 parts of dispersant, 0.6-0.7 parts of accelerator, 0.6-1.0 parts of bridging agent, 2.3-2.7 parts of foaming agent and 5-7 parts of titanium dioxide according to weight parts, and set aside; Step 2: Add ethylene-vinyl acetate copolymer, dual antibacterial material, toughening agent, flow agent, anti-shrinkage agent, talcum powder, nucleating agent, dispersant, accelerator, bridging agent, foaming agent and titanium dioxide into a high-speed mixer, stir and mix for 10-20 minutes at a temperature of 25-30° C. and a stirring rate of 800-1200 r / min to obtain a premix; Step 3: Add the premix to a twin-screw extruder, melt-extrude at a temperature of 150-180° C. and a screw speed of 150-200 r / min, and granulate to obtain an integrally formed polymer microporous foam slipper material.

10. The method for preparing an integrally formed polymer microporous foamed slipper material according to claim 9, characterized in that: The ethylene-vinyl acetate copolymer is Formosa Plastics EVA7470M; The toughening agent is POE-LC168 toughening agent; The flow agent is HZ-303PP flow agent; The anti-shrinkage agent is JQ9107 anti-shrinkage agent; The nucleating agent is magnesium oxide; The dispersant is zinc stearate; The accelerator is stearic acid; The bridging agent is a BIBP bridging agent; The foaming agent is an AC foaming agent.

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