An anti-fall and antibacterial foamed insole and its preparation method and application

Abstract

The present invention relates to the technical field of EVA, and discloses a fall-proof and antibacterial foamed insole and its preparation method and application. The foamed insole comprises the following components in parts by weight: 100 parts of ethylene-vinyl acetate copolymer, 1-8 parts of hydroxy-containing polyquaternary ammonium salt, 0.6-5 parts of acrylic acid hydroxyethyl ester grafted EVA, 0.8-7 parts of terminal isocyanate polyurethane, 4-5.5 parts of foaming agent, 0.8-1.5 parts of auxiliary agent, and 1.2-1.7 parts of crosslinking agent; during high-temperature mixing and molding, the hydroxy groups of the hydroxy-containing polyquaternary ammonium salt and the acrylic acid hydroxyethyl ester grafted EVA react with the terminal isocyanate groups of the polyurethane, so that the three form a chemically crosslinked hybrid system, making the insole material exhibit higher tear strength, tensile strength and elongation at break, and at the same time having good hydrophilicity and antibacterial and mildew-proof properties.

Description

Technical Field

[0001] The present invention relates to the technical field of EVA, and specifically relates to a fall-proof and antibacterial foamed insole and its preparation method and application. Background Art

[0002] Ethylene-vinyl acetate copolymer EVA is a general-purpose polymer with good elasticity, flexibility, high gloss, and low cost, and has extensive applications in the shoemaking industry such as soles and insoles. Improving its mechanical properties such as strength and toughness can enable EVA to have better practical applications in materials such as insoles. Traditional EVA insoles have poor hydrophilic and moisture-absorbing properties, poor moisture-permeable properties, and are prone to mold and bacteria growth during long-term wear, presenting safety and health problems.

[0003] Quaternary ammonium salt macromolecular polymers have good antibacterial properties, good heat resistance, and are not easily decomposed, and have extensive applications in polymer materials. Patent CN118006032B discloses that using quaternary ammonium salt chitosan, polyvinyl alcohol, tetraethyl orthosilicate, coupling agents, etc. as raw materials, a composite antibacterial agent is prepared and mixed with an EVA resin plastic matrix and an EVA-g-MAH compatibilizer to obtain an antibacterial plastic injection molding. However, this EVA plastic injection molding does not have good hydrophilicity, which is not conducive to the practical application of EVA in hydrophilic and moisture-permeable insoles. Summary of the Invention

[0004] The technical problem solved by the present invention is: to improve the mechanical strength, antibacterial and mildew-proof properties, and hydrophilicity of the EVA foamed insole material.

[0005] The technical solution of the present invention: A fall-proof and antibacterial foamed insole, comprising the following components in parts by weight, 100 parts of ethylene-vinyl acetate copolymer, 1-8 parts of hydroxy-containing polyquaternary ammonium salt, 0.6-5 parts of acrylic acid hydroxyethyl ester grafted EVA, 0.8-7 parts of terminal isocyanate polyurethane, 4-5.5 parts of foaming agent, 0.8-1.5 parts of auxiliary agent, 1.2-1.7 parts of crosslinking agent.

[0006] Preferably, the preparation method of the hydroxy-containing polyquaternary ammonium salt includes: adding 1,3-dichloro-2-propanol and N,N-bis[2-(dimethylamino)ethyl] terephthalamide in a molar ratio of 1:(0.8-1.2) to isopropanol, stirring and refluxing at a temperature of 80-85°C for 48-60h, rotary evaporating the solution, washing with acetone, and drying to obtain the hydroxy-containing polyquaternary ammonium salt. The reaction formula is as follows:

[0007]

[0008] Preferably, the preparation method of N,N-bis[2-(dimethylamino)ethyl]terephthalamide includes: adding terephthaloyl chloride, N,N-dimethylethylenediamine, and pyridine with a molar ratio of 1:(1.8 - 2.2):(2 - 2.2) into tetrahydrofuran, stirring at room temperature for reaction for 6 - 10 h, rotary evaporating the solution, separating by silica gel column chromatography, and eluting with a solution of ethyl acetate and petroleum ether to obtain N,N-bis[2-(dimethylamino)ethyl]terephthalamide. The reaction formula is as follows:

[0009]

[0010] Preferably, the preparation method of terminal isocyanate polyurethane includes: drying and dehydrating polyethylene glycol, then mixing it with diisocyanate with a molar ratio of 1:(2.1 - 2.2), reacting at 65 - 70 °C for 2 - 3 h in a nitrogen atmosphere, and cooling to obtain terminal isocyanate polyurethane.

[0011] Preferably, the diisocyanate is isophorone diisocyanate, toluene-2,4-diisocyanate or diphenylmethane-4,4'-diisocyanate.

[0012] Preferably, the blowing agent is azodicarbonamide and the crosslinking agent is dicumyl peroxide.

[0013] Preferably, the additives include zinc stearate, stearic acid or a combination thereof.

[0014] Preferably, the preparation method of hydroxyethyl acrylate grafted EVA includes: mixing ethylene-vinyl acetate copolymer, hydroxyethyl acrylate, and dicumyl peroxide in a mixer according to a mass ratio of 100:(2 - 7):(0.12 - 0.46), then performing melt grafting in a single-screw extruder, with a melt temperature of 160 - 170 °C, a screw speed of 30 - 50 r / min, and extruding to obtain hydroxyethyl acrylate grafted EVA.

[0015] Preferably, the preparation method of the anti-fall and antibacterial foamed insole includes: placing ethylene-vinyl acetate copolymer, hydroxyl-containing polyquaternary ammonium salt, hydroxyethyl acrylate grafted EVA, terminal isocyanate polyurethane, and additives in a kneader, kneading at 110 - 120 °C for 10 - 15 min, then adding a crosslinking agent and a blowing agent, and kneading for 3 - 5 min; placing the material in an open mill for kneading, making a triangular package, thin passing, and cooling to produce a sheet; finally, molding in a flat vulcanizing machine for 40 - 60 min, controlling the pressure at 12 - 18 MPa and the temperature at 160 - 170 °C to obtain the anti-fall and antibacterial foamed insole.

[0016] Preferably, a dot convex matrix is arranged on the lower surface of the anti-fall and antibacterial foamed insole to increase the friction between the insole and the sole and improve the anti-slip and anti-fall performance.

[0017] The technical effects produced by the present invention are as follows: In the present invention, 1,3-dichloro-2-propanol and N,N-bis[2-(dimethylamino)ethyl]terephthalamide are subjected to quaternization reaction and polymerized to obtain a hydroxyl-containing polyquaternary ammonium salt.

[0018] The present invention uses ethylene-vinyl acetate copolymer EVA as the basis of the foamed insole material, and adds a hydroxyl-containing polyquaternary ammonium salt, hydroxyethyl acrylate grafted EVA, terminal isocyanate polyurethane, a foaming agent, a crosslinking agent, etc. During the high-temperature mixing and molding process, the hydroxyl groups of the hydroxyl-containing polyquaternary ammonium salt and hydroxyethyl acrylate grafted EVA react with the terminal isocyanate groups of the polyurethane, causing the three to form a chemically crosslinked hybrid system. The crosslinked hybrid system contains an EVA component, which can act as a compatibilizer, improving the compatibility between the crosslinked hybrid system and the ethylene-vinyl acetate copolymer EVA substrate. The polyurethane in the crosslinked hybrid system has good toughness and has a good toughening effect on the EVA insole material. At the same time, the main chain of the hydroxyl-containing polyquaternary ammonium salt contains a rigid benzene ring, which is beneficial to improving the strength of the EVA insole material. Under the synergistic effect, the insole material exhibits higher tear strength, tensile strength, and elongation at break.

[0019] The present invention adds a hydroxyl-containing polyquaternary ammonium salt to the EVA foamed insole material. It contains hydrophilic groups such as hydroxyl groups, quaternary ammonium salt cations, and amide groups, which can improve the hydrophilicity of the insole material and is beneficial to improving the moisture absorption and moisture permeability performance of the insole material. And the main chain of the molecule contains a large number of antibacterial quaternary ammonium salt groups, showing a high antibacterial zone and antibacterial and bactericidal effects against bacteria and molds such as Staphylococcus aureus, Candida albicans, Penicillium, and Aspergillus niger, significantly improving the antibacterial and antifungal properties of the foamed insole material.

[0020] The present invention sets a dot convex matrix on the lower surface of the anti-drop and antibacterial foamed insole to increase the friction between the insole and the sole and improve the anti-slip and anti-drop performance. Specific Embodiments

[0021] The following further describes the embodiments of the present invention in detail in conjunction with the examples. The detailed description of the following examples is used to exemplarily illustrate the principle of the present invention, but cannot be used to limit the scope of the present invention, that is, the present invention is not limited to the described embodiments.

[0022] Example 1

[0023] (1) Add 15 mmol of terephthaloyl chloride, 30 mmol of N,N-dimethylethylenediamine, and 33 mmol of pyridine to 30 mL of tetrahydrofuran, stir and react at room temperature for 6 h, rotary evaporate the solution, and separate by silica gel column chromatography, eluting with a solution of ethyl acetate and petroleum ether to obtain N,N-bis[2-(dimethylamino)ethyl]terephthalamide.

[0024] (2) Add 20 mmol of 1,3-dichloro-2-propanol and 20 mmol of N,N-bis[2-(dimethylamino)ethyl]terephthalamide to 40 mL of isopropanol, stir at 85 °C and reflux for 60 h, rotary evaporate the solution, wash with acetone, and dry to obtain hydroxy-containing polyquaternary ammonium salt.

[0025] (3) Dry and remove water from 30 mmol of polyethylene glycol 1000, then mix it with 66 mmol of diphenylmethane-4,4'-diisocyanate, react at 65 °C for 3 h in a nitrogen atmosphere, and cool to obtain terminal isocyanate polyurethane.

[0026] (4) Mix 50 g of ethylene-vinyl acetate copolymer, 1 g of hydroxyethyl acrylate, and 0.06 g of diisopropylbenzene peroxide in a mixer, then perform melt grafting on a single-screw extruder, with a melting temperature of 170 °C and a screw speed of 30 r / min, and extrude to obtain hydroxyethyl acrylate-grafted EVA.

[0027] (5) Place 1000 g of ethylene-vinyl acetate copolymer, 10 g of hydroxy-containing polyquaternary ammonium salt, 6 g of hydroxyethyl acrylate-grafted EVA, 8 g of terminal isocyanate polyurethane, 5.3 g of zinc stearate as an additive and 6.2 g of stearic acid in a kneader, knead at 110 °C for 15 min, then add 12 g of crosslinking agent diisopropylbenzene peroxide and 44 g of blowing agent azodicarbonamide, and knead for 3 min; place the material on an open mill for kneading, make triangular packages, thin pass, and cool to produce sheets; finally, mold at 12 MPa and 170 °C for 60 min in a flat vulcanizer, and set a dot convex matrix on the lower surface of the foamed insole to obtain a shockproof and antibacterial foamed insole material.

[0028] Example 2

[0029] (1) Add 15 mmol of terephthaloyl chloride, 33 mmol of N,N-dimethylethylenediamine, and 33 mmol of pyridine to 40 mL of tetrahydrofuran, stir at room temperature for 6 h, rotary evaporate the solution, separate by silica gel column chromatography, and elute with a solution of ethyl acetate and petroleum ether to obtain N,N-bis[2-(dimethylamino)ethyl]terephthalamide.

[0030] (2) Add 20 mmol of 1,3-dichloro-2-propanol and 24 mmol of N,N-bis[2-(dimethylamino)ethyl]terephthalamide to 50 mL of isopropanol, stir at 85 °C and reflux for 48 h, rotary evaporate the solution, wash with acetone, and dry to obtain hydroxy-containing polyquaternary ammonium salt.

[0031] (3) 30 mmol of polyethylene glycol 1000 was dried to remove water, then mixed with 63 mmol of isophorone diisocyanate, and reacted at 70 °C for 2 h in a nitrogen atmosphere. After cooling, the terminal isocyanate polyurethane was obtained.

[0032] (4) 50 g of ethylene-vinyl acetate copolymer, 2.2 g of 2-hydroxyethyl acrylate, and 0.15 g of diisopropylbenzene peroxide were mixed evenly in a mixer, and then melt grafted in a single-screw extruder. The melting temperature was 160 °C, the screw speed was 50 r / min, and extrusion was carried out to obtain 2-hydroxyethyl acrylate grafted EVA.

[0033] (5) 1000 g of ethylene-vinyl acetate copolymer, 40 g of hydroxyl-containing polyquaternary ammonium salt, 25 g of 2-hydroxyethyl acrylate grafted EVA, 36 g of terminal isocyanate polyurethane, 6.7 g of zinc stearate as an additive and 8.3 g of stearic acid were placed in a kneader and kneaded at 120 °C for 15 min. Then 12 g of crosslinking agent diisopropylbenzene peroxide and 40 g of foaming agent azodicarbonamide were added and kneaded for 5 min; the material was placed in an open mill for kneading, making triangular packages, thin passing, and cooling to produce sheets; finally, it was molded in a flat vulcanizer for 60 min, controlling the pressure at 18 MPa and the temperature at 160 °C, and a dot convex matrix was set on the lower surface of the foamed insole to obtain the anti-fall and antibacterial foamed insole material.

[0034] Example 3

[0035] (1) 15 mmol of terephthaloyl chloride, 27 mmol of N,N-dimethylethylenediamine, and 30 mmol of pyridine were added to 30 mL of tetrahydrofuran, and the reaction was carried out by stirring at room temperature for 10 h. The solution was rotary evaporated and separated by silica column chromatography, and eluted with a solution of ethyl acetate and petroleum ether to obtain N,N-bis[2-(dimethylamino)ethyl]terephthalamide.

[0036] (2) 20 mmol of 1,3-dichloro-2-propanol and 16 mmol of N,N-bis[2-(dimethylamino)ethyl]terephthalamide were added to 40 mL of isopropanol, and the reaction was carried out by stirring and refluxing at 80 °C for 60 h. The solution was rotary evaporated, washed with acetone, and dried to obtain the hydroxyl-containing polyquaternary ammonium salt.

[0037] (3) 30 mmol of polyethylene glycol 1000 was dried to remove water, then mixed with 66 mmol of toluene-2,4-diisocyanate, and reacted at 70 °C for 2 h in a nitrogen atmosphere. After cooling, the terminal isocyanate polyurethane was obtained.

[0038] (4) Mix 50 g of ethylene-vinyl acetate copolymer, 3.5 g of 2-hydroxyethyl acrylate, and 0.23 g of diisopropylbenzene peroxide in a mixer, and then perform melt grafting on a single-screw extruder. The melting temperature is 165 °C, the screw speed is 50 r / min, and then extrude to obtain 2-hydroxyethyl acrylate grafted EVA.

[0039] (5) Place 1000 g of ethylene-vinyl acetate copolymer, 80 g of hydroxyl-containing polyquaternary ammonium salt, 50 g of 2-hydroxyethyl acrylate grafted EVA, 70 g of terminal isocyanate polyurethane, 4.6 g of zinc stearate as an additive and 3.4 g of stearic acid in a kneader, knead at 120 °C for 10 min, then add 17 g of crosslinking agent diisopropylbenzene peroxide and 55 g of foaming agent azodicarbonamide, and knead for 3 min; Place the material in an open mill for kneading, make triangular packages, thin pass, cool and sheet out; Finally, mold in a flat vulcanizer for 40 min, control the pressure at 15 MPa and the temperature at 170 °C, and set a dot convex matrix on the lower surface of the foamed insole to obtain an anti-fall and antibacterial foamed insole material.

[0040] Comparative Example 1

[0041] (1) Place 1000 g of ethylene-vinyl acetate copolymer, 5.3 g of zinc stearate as an additive and 6.2 g of stearic acid in a kneader, knead at 110 °C for 15 min, then add 12 g of crosslinking agent diisopropylbenzene peroxide and 44 g of foaming agent azodicarbonamide, and knead for 3 min; Place the material in an open mill for kneading, make triangular packages, thin pass, cool and sheet out; Finally, mold in a flat vulcanizer for 60 min, control the pressure at 12 MPa and the temperature at 170 °C, and set a dot convex matrix on the lower surface of the foamed insole to obtain an anti-fall and antibacterial foamed insole material.

[0042] Comparative Example 2

[0043] (1) Place 1000 g of ethylene-vinyl acetate copolymer, 6 g of 2-hydroxyethyl acrylate grafted EVA, 8 g of terminal isocyanate polyurethane, 5.3 g of zinc stearate as an additive and 6.2 g of stearic acid in a kneader, knead at 110 °C for 15 min, then add 12 g of crosslinking agent diisopropylbenzene peroxide and 44 g of foaming agent azodicarbonamide, and knead for 3 min; Place the material in an open mill for kneading, make triangular packages, thin pass, cool and sheet out; Finally, mold in a flat vulcanizer for 60 min, control the pressure at 12 MPa and the temperature at 170 °C, and set a dot convex matrix on the lower surface of the foamed insole to obtain an anti-fall and antibacterial foamed insole material.

[0044] Comparative Example 3

[0045] (1) Put 1000 g of ethylene-vinyl acetate copolymer, 10 g of hydroxyl-containing polyquaternary ammonium salt, 8 g of terminal isocyanate polyurethane, 5.3 g of zinc stearate as an additive and 6.2 g of stearic acid into a kneader, knead at 110 °C for 15 min, then add 12 g of crosslinking agent dicumyl peroxide and 44 g of blowing agent azodicarbonamide, and knead for 3 min; place the material in an open mill for kneading, make triangular bales, thin pass, cool and sheet out; finally, mold in a flat vulcanizer for 60 min, control the pressure at 12 MPa and the temperature at 170 °C, and set a dot convex matrix on the lower surface of the foamed insole to obtain an anti-fall and antibacterial foamed insole material.

[0046] Comparative Example 4

[0047] (1) Put 1000 g of ethylene-vinyl acetate copolymer, 10 g of hydroxyl-containing polyquaternary ammonium salt, 6 g of hydroxyethyl acrylate-grafted EVA, 5.3 g of zinc stearate as an additive and 6.2 g of stearic acid into a kneader, knead at 110 °C for 15 min, then add 12 g of crosslinking agent dicumyl peroxide and 44 g of blowing agent azodicarbonamide, and knead for 3 min; place the material in an open mill for kneading, make triangular bales, thin pass, cool and sheet out; finally, mold in a flat vulcanizer for 60 min, control the pressure at 12 MPa and the temperature at 170 °C, and set a dot convex matrix on the lower surface of the foamed insole to obtain an anti-fall and antibacterial foamed insole material.

[0048] Comparative Example 5

[0049] (1) Add 20 mmol of 1,3-dichloropropane and 20 mmol of N,N-bis[2-(dimethylamino)ethyl]terephthalamide to 40 mL of isopropanol, stir and reflux at 85 °C for 60 h, rotate-evaporate the solution, wash with acetone, and dry to obtain polyquaternary ammonium salt-containing.

[0050] (2) Put 1000 g of ethylene-vinyl acetate copolymer, 10 g of polyquaternary ammonium salt-containing, 6 g of hydroxyethyl acrylate-grafted EVA, 8 g of terminal isocyanate polyurethane, 5.3 g of zinc stearate as an additive and 6.2 g of stearic acid into a kneader, knead at 110 °C for 15 min, then add 12 g of crosslinking agent dicumyl peroxide and 44 g of blowing agent azodicarbonamide, and knead for 3 min; place the material in an open mill for kneading, make triangular bales, thin pass, cool and sheet out; finally, mold in a flat vulcanizer for 60 min, control the pressure at 12 MPa and the temperature at 170 °C, and set a dot convex matrix on the lower surface of the foamed insole to obtain an anti-fall and antibacterial foamed insole material.

[0051] Use a universal tensile testing machine to test the tensile strength and elongation at break according to the GB / T 6344-2008 standard. Test the tear strength of the insole material according to the GB / T 10808-2006 standard.

[0052] The water contact angle of the insole material surface was measured using a contact angle measuring instrument. Each sample was measured 5 times and the average value was taken.

[0053] Table 1 Performance Test of Insole Materials

[0054]

[0055]

[0056] As can be seen from Table 1, compared with Comparative Example 1, in the EVA insole materials of Examples 1-3, hydroxy-containing polyquaternary ammonium salt, hydroxyethyl acrylate-grafted EVA, and terminal isocyanate polyurethane were added. During the high-temperature mixing and molding processes, the hydroxyl groups of the hydroxy-containing polyquaternary ammonium salt and hydroxyethyl acrylate-grafted EVA reacted with the terminal isocyanate groups of the polyurethane, causing the three to form a chemically crosslinked hybrid system. The crosslinked hybrid system contains an EVA component, which can act as a compatibilizer, improving the compatibility between the crosslinked hybrid system and ethylene-vinyl acetate copolymer (EVA). The polyurethane in the crosslinked hybrid system has good toughness and has a good toughening effect on the EVA insole material. At the same time, the main chain of the hydroxy-containing polyquaternary ammonium salt contains a rigid benzene ring, which is beneficial to improving the strength of the EVA insole material. Under the synergistic effect, the insole material exhibits higher tear strength, tensile strength, and elongation at break. And the hydroxy-containing polyquaternary ammonium salt contains hydrophilic groups such as hydroxyl groups, quaternary ammonium salt cations, and amide groups, which can improve the hydrophilicity of the insole material and is beneficial to improving the moisture absorption and moisture permeability performance of the insole material.

[0057] Compared with Example 1, Comparative Example 2 did not add hydroxy-containing polyquaternary ammonium salt, and its tear strength and tensile strength were lower than those of Example 1, and the water contact angle was larger, indicating poor hydrophilic performance.

[0058] Compared with Example 1, Comparative Example 3 did not add hydroxyethyl acrylate-grafted EVA. Although the hydroxy-containing polyquaternary ammonium salt and terminal isocyanate polyurethane can undergo a crosslinking reaction, the formed crosslinked hybrid system does not contain an EVA structure, resulting in poor compatibility between the crosslinked hybrid system and the EVA foaming material, and poor strengthening and toughening effects. The tear strength, tensile strength, and elongation at break are significantly lower than those of Example 1.

[0059] Compared with Example 1, Comparative Example 4 did not add terminal isocyanate polyurethane and could not undergo a crosslinking reaction with the hydroxy-containing polyquaternary ammonium salt and hydroxyethyl acrylate-grafted EVA, resulting in the hydroxyethyl acrylate-grafted EVA not acting as a compatibilizer and not improving the compatibility between the hydroxy-containing polyquaternary ammonium salt and the EVA foaming material. The tear strength, tensile strength, and elongation at break are significantly lower than those of Example 1.

[0060] Compared with Example 1, in Comparative Example 5, 1,3-dichloropropane was reacted with N,N-bis[2-(dimethylamino)ethyl]terephthalamide, and the obtained polyquaternary ammonium salt-containing product did not contain hydroxyl groups and could not crosslink with terminal isocyanate polyurethane and acrylic hydroxyethyl grafted EVA, resulting in poor compatibility between the polyquaternary ammonium salt-containing product and the EVA foaming material, and the tear strength, tensile strength and elongation at break were lower than those in Example 1.

[0061] Staphylococcus aureus, Candida albicans, Penicillium and Aspergillus niger were used as test bacteria and molds respectively. The antibacterial properties of the insole materials against bacteria and molds were tested by the diameter of the inhibition zone method.

[0062] The insole materials were pressed into film specimens with a thickness of 1 mm. 0.2 mL of the activated bacterial or mold liquid was pipetted and coated on the surface of the culture medium, and then cultured in a constant temperature incubator. After culturing, the diameter of the inhibition zone was measured. Each group of specimens was tested 3 times and the average value was taken.

[0063] Among them, the concentration of the activated liquid of Staphylococcus aureus and Candida albicans was 10 7 cfu / mL, the culture medium was beef extract peptone culture, the temperature during culture was 37 °C, and the time was 24 h.

[0064] The culture medium for Penicillium and Aspergillus niger was potato culture medium. The spore concentration of the mold liquid was 10 6 cells / mL, the temperature during culture was 28 °C, and the time was 48 h.

[0065] Table 2 Antibacterial and antifungal performance test of insole materials

[0066]

[0067] It can be seen from Table 2 that in Examples 1-3 and Comparative Examples 3-4, hydroxy-containing polyquaternary ammonium salts were added, and in Comparative Example 5, polyquaternary ammonium salts were added. The main chain of its molecule contains a large number of antibacterial quaternary ammonium salt groups, showing a high inhibition zone and antibacterial and bactericidal effects on bacteria and molds such as Staphylococcus aureus, Candida albicans, Penicillium and Aspergillus niger, and significantly improving the antibacterial and antifungal properties of the EVA foaming insole materials.

[0068] The above are only the embodiments of the present application and do not limit the present application. For those skilled in the art, the present application can have various changes and modifications without departing from the scope of the present invention. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present application shall be included within the scope of the claims of the present application.

Claims

1. A fall-proof and antibacterial foamed insole, characterized in that it comprises the following components in parts by weight: 100 parts of ethylene-vinyl acetate copolymer, 1-8 parts of hydroxy-containing polyquaternary ammonium salt, 0.6-5 parts of hydroxyethyl acrylate grafted EVA, 0.8-7 parts of terminal isocyanate polyurethane, 4-5.5 parts of foaming agent, 0.8-1.5 parts of auxiliary agent, 1.2-1.7 parts of crosslinking agent; The preparation method of the hydroxy-containing polyquaternary ammonium salt includes: adding 1,3-dichloro-2-propanol and N,N-bis[2-(dimethylamino)ethyl] terephthalamide in a molar ratio of 1:(0.8-1.2) to isopropanol, stirring for reaction, rotary evaporating the solution, washing with acetone, and drying to obtain the hydroxy-containing polyquaternary ammonium salt; The preparation method of N,N-bis[2-(dimethylamino)ethyl] terephthalamide includes: adding terephthaloyl chloride, N,N-dimethylethylenediamine, and pyridine in a molar ratio of 1:(1.8-2.2):(2-2.2) to tetrahydrofuran, stirring at room temperature for reaction for 6-10 h, rotary evaporating the solution, separating by silica gel column chromatography, and eluting with a solution of ethyl acetate and petroleum ether to obtain N,N-bis[2-(dimethylamino)ethyl] terephthalamide; The preparation method of the hydroxyethyl acrylate grafted EVA includes: mixing ethylene-vinyl acetate copolymer, hydroxyethyl acrylate, and diisopropylbenzene peroxide in a mass ratio of 100:(2-7):(0.12-0.46) in a mixer, and then performing melt grafting in a single-screw extruder, with a melting temperature of 160-170 °C, a screw rotation speed of 30-50 r / min, and extruding to obtain the hydroxyethyl acrylate grafted EVA.

2. The fall-proof and antibacterial foamed insole according to claim 1, characterized in that in the preparation method of the hydroxy-containing polyquaternary ammonium salt, the reaction is carried out under reflux condensation at a temperature of 80-85 °C for 48-60 h.

3. The fall-proof and antibacterial foamed insole according to claim 1, characterized in that the preparation method of the terminal isocyanate polyurethane includes: drying and dehydrating polyethylene glycol, and then mixing it with diisocyanate, with a molar ratio of the two being 1:(2.1-2.2), reacting in a nitrogen atmosphere at 65-70 °C for 2-3 h, and cooling to obtain the terminal isocyanate polyurethane.

4. The fall-proof and antibacterial foamed insole according to claim 3, characterized in that the diisocyanate is isophorone diisocyanate, toluene-2,4-diisocyanate or diphenylmethane-4,4'-diisocyanate.

5. The fall-proof and antibacterial foamed insole according to claim 1, characterized in that the foaming agent is azodicarbonamide, and the crosslinking agent is diisopropylbenzene peroxide.

6. The fall-proof and antibacterial foamed insole according to claim 1, characterized in that the auxiliary agent includes one or a combination of zinc stearate and stearic acid.

7. A preparation method of a fall-proof and antibacterial foamed insole according to any one of claims 1-6, characterized in that The preparation method includes: putting ethylene-vinyl acetate copolymer, hydroxyl-containing polyquaternary ammonium salt, acrylic acid hydroxyethyl ester grafted EVA, terminal isocyanate polyurethane, and additives into a mixer, mixing at 110-120°C for 10-15 minutes, then adding a crosslinking agent and a foaming agent, and mixing for 3-5 minutes; putting the material into an open mill for mixing, making triangular packages, passing thinly, and cooling to produce sheets; finally, molding in a flat vulcanizing machine for 40-60 minutes, controlling the pressure at 12-18 MPa and the temperature at 160-170°C to obtain an anti-fall and antibacterial foamed insole.

8. The anti-fall and antibacterial foamed insole obtained by the preparation method according to claim 7, characterized in that a dot protrusion matrix is arranged on the lower surface of the anti-fall and antibacterial foamed insole to increase the friction between the insole and the sole.

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