A wear-resistant waterproof shoe sole material and a preparation method thereof

Abstract

The present application relates to polyurethane shoe sole technical field, and disclose a kind of wear-resistant waterproof shoe sole material and preparation method, the wear-resistant waterproof shoe sole material of the present application includes 100 weight parts polyester polyol, 2-8 weight parts modified nylon fiber, 5.2-6.4 weight parts chain extender, 17-24 weight parts foaming agent, 113-124 weight parts isocyanate substance etc.;Nylon fiber is introduced after grafting modification a large number of benzene ring structure on the surface of fiber, and benzene ring in polyurethane molecular chain forms π-π bond interaction, improves the interface force between fiber and polyurethane, it is favorable to improve the wear resistance of shoe sole material, reduce relative volume abrasion loss, improve tear strength and compressive strength.Graft a large number of hydrophobic siloxane and benzene ring structure on the surface of nylon fiber, can form hydrophobic network in shoe sole material matrix, reduce water absorption, improve water resistance and waterproof performance.

Description

Technical Field

[0001] This invention relates to the field of polyurethane shoe sole technology, specifically to a wear-resistant and waterproof shoe sole material and its preparation method. Background Technology

[0002] Polyurethane foam (PU) possesses high elasticity, excellent shock absorption and compression resistance, and superior corrosion resistance, making it widely used in footwear, insulation materials, and building materials. However, PU foam exhibits relatively low mechanical strength and poor abrasion resistance, hindering the development of high-performance shoe sole materials. Reinforcing and modifying PU foam with polymer fibers, carbon fibers, and nanoparticles can improve its mechanical strength and abrasion resistance.

[0003] Nylon fibers possess advantages such as high wear resistance, high modulus, and high strength, making them important in polymer materials such as foamed plastics and rubber. Chinese patent CN112679941B discloses a high-strength sound-insulating polyurethane urea composite material. This material incorporates polyurethane microspheres, nylon fibers, and aramid fibers as reinforcing fibers, improving the dispersion and reinforcing effect of hollow inorganic fillers. However, the nylon and other fibers in this patent do not reduce the water absorption rate of the polyurethane material or improve its water resistance, which is detrimental to the practical application of polyurethane materials in shoe soles. Summary of the Invention

[0004] To address the shortcomings of existing technologies, this invention provides a wear-resistant and waterproof shoe sole material and its preparation method, solving the problem of poor mechanical strength and wear resistance of polyurethane shoe sole materials.

[0005] The technical solution of the present invention is: a wear-resistant and waterproof shoe sole material and a preparation method thereof, wherein the shoe sole material comprises 100 parts by weight of polyester polyol, 2-8 parts by weight of modified nylon fiber, 5.2-6.4 parts by weight of chain extender, 17-24 parts by weight of foaming agent, 2-5.6 parts by weight of foam leveling agent, 1.5-3 parts by weight of catalyst, 1.4-2.2 parts by weight of water, and 113-124 parts by weight of isocyanate substance.

[0006] The preparation method of wear-resistant and waterproof shoe sole material is as follows:

[0007] (1) Add potassium persulfate aqueous solution and cleaned nylon fiber to a flask, place it in a microwave reactor for pre-initiation reaction, then add the fiber to an aqueous solution containing allyloxy pentaerythritol, place it in a microwave reactor for grafting reaction, filter, wash the fiber with water and ethanol, then extract it with acetone in a Soxhlet extractor, dry it to obtain allyl pentaerythritol grafted nylon fiber.

[0008] (2) Add dichloromethane and allyl pentaerythritol-grafted nylon fibers to a flask, stir, add phenylchlorosilane compound, 4-dimethylaminopyridine and triethylamine, stir and react, filter, wash the fibers with dichloromethane and ethanol, dry, and obtain modified nylon fibers.

[0009] (3) Mix polyester polyol, modified nylon fiber, chain extender, foaming agent, foam leveling agent, catalyst and water, then mix with isocyanate, add to mold, foam at 20-40℃, and then cure at 25-70℃ for 12-36h to obtain wear-resistant and waterproof shoe sole material.

[0010] Preferably, the chain extender is any one or a combination of 1,4-butanediol and triethanolamine.

[0011] Preferably, the isocyanate is any one or a combination of polymethylene polyphenyl polyisocyanate and diphenylmethane diisocyanate.

[0012] Preferably, the catalyst is any one or a combination of triethylenediamine, pentamethyldiethylenetriamine, and dibutyltin dilaurate.

[0013] Preferably, the foam stabilizer is silicone oil.

[0014] Preferably, the foaming agent is dichlorofluoroethane.

[0015] Preferably, in (1), the concentration of potassium persulfate aqueous solution is 15-50 mmol / L; and the concentration of allyloxypentaerythritol aqueous solution is 0.4-1 mol / L.

[0016] Preferably, in (1), the microwave power during the pre-initiation reaction is 300-600W, the temperature is 65-70℃, and the reaction time is 20-40min.

[0017] Preferably, the microwave power during the grafting reaction is 300-600W, the temperature is 65-80℃, and the reaction time is 1-2h.

[0018] Preferably, in (2), the mass ratio of allyl pentaerythritol-grafted nylon fiber, phenylchlorosilane compound, 4-dimethylaminopyridine, and triethylamine is 100:(6-30):(3.8-13.6):(3.2-12.6).

[0019] Preferably, in (2), the phenylchlorosilane compound is phenyldimethylchlorosilane, diphenylchlorosilane or triphenylchlorosilane.

[0020] Preferably, in (2), the reaction temperature is 20-30℃ and the reaction time is 24-36h.

[0021] The beneficial technical effects of this invention are as follows: By using allyloxy pentaerythritol to perform a microwave grafting reaction on nylon fibers, a large number of hydroxyl groups are introduced into the surface of the nylon fibers. Then, the hydroxyl groups react with the Si-Cl bonds of phenylchlorosilane compounds, thereby introducing a large number of siloxane and phenyl structures into the surface of the nylon fibers. Finally, the nylon fibers, polyester polyols, foaming agents, catalysts, isocyanate substances, etc. are blended and foamed to obtain a wear-resistant and waterproof shoe sole material.

[0022] The nylon fibers of this invention, after graft modification, introduce a large number of benzene ring structures on the fiber surface, which interact with the benzene rings in the polyurethane molecular chain through π-π bonds. This enhances the interfacial force between the fiber and the polyurethane, which is beneficial for improving the abrasion resistance of the shoe sole material and reducing the relative volumetric abrasion loss. Furthermore, the improved compatibility between the nylon fibers and the polyurethane matrix, along with their uniform dispersion in the foamed shoe sole material, significantly improves the mechanical properties of the material, notably increasing tear strength and compressive strength.

[0023] This invention grafts a large number of hydrophobic siloxanes and benzene ring structures onto the surface of nylon fibers, which can form a hydrophobic network in the shoe sole material matrix, reduce water absorption, and improve water resistance and waterproof performance. Detailed Implementation

[0024] To make the technical problems solved, technical solutions, and beneficial effects of the present invention clearer, the present invention will be further described in detail below with reference to embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the present invention and are not intended to limit the present invention.

[0025] Allyloxypentaerythritol was prepared according to the method described in the journal Chem. Commun., 2018, 54, 3875-3878, "In vivodrug tracking with 19F MRI at therapeutic dose". 200 mL of water, 9.6 g of sodium hydroxide, and 68 g of pentaerythritol were added to a flask. After stirring, 24.2 g of bromopropene was added dropwise. The mixture was heated to 70 °C and stirred for 8 h. 100 mL of water was added, and the mixture was extracted with ethyl acetate. The organic layer was distilled under reduced pressure. The crude product was separated by silica gel column chromatography and eluted with petroleum ether and ethyl acetate to obtain allyloxypentaerythritol, with the structural formula [insert structural formula here]. .

[0026] The following polyester polyol is designated as Jining Fangyu Chemical YHY450C. The nylon fiber is nylon 66 fiber with a length of 3mm.

[0027] Example 1:

[0028] (1) Add 1L of potassium persulfate aqueous solution with a concentration of 15mmol / L and 40g of cleaned nylon fiber to a flask, place it in a microwave reactor for a pre-initiation reaction for 20min, control the microwave power to be 500W and the temperature to be 70℃; then add the fiber to 1L of allyloxypentaerythritol aqueous solution with a concentration of 0.4mol / L, place it in a microwave reactor for a grafting reaction for 1h, control the microwave power to be 500W and the temperature to be 80℃, filter, wash the fiber with water and ethanol, then extract it with acetone in a Soxhlet extractor, dry it, and obtain allyl pentaerythritol grafted nylon fiber.

[0029] (2) Add 1L of dichloromethane and 50g of allyl pentaerythritol-grafted nylon fiber to a flask, stir, and then add 3g of diphenylchlorosilane, 1.9g of 4-dimethylaminopyridine and 1.6g of triethylamine. Stir and react at 25°C for 24h, filter, wash the fiber with dichloromethane and ethanol, and dry to obtain modified nylon fiber.

[0030] (3) Mix 500g polyester polyol, 10g modified nylon fiber, 27.5g 1,4-butanediol, 98g dichlorofluoroethane, 17g silicone oil, 11.3g triethylenediamine, 1.2g dibutyltin dilaurate and 10g water, then mix with 565g polymethylene polyphenyl polyisocyanate, add to a mold, foam at 30°C, and then cure at 40°C for 24 hours to obtain wear-resistant and waterproof shoe sole material.

[0031] Example 2:

[0032] (1) Add 1L of 50mmol / L potassium persulfate aqueous solution and 40g of cleaned nylon fiber to a flask, place it in a microwave reactor for a pre-initiation reaction for 40min, control the microwave power to be 300W and the temperature to be 70℃; then add the fiber to 1L of 1mol / L allyloxypentaerythritol aqueous solution, place it in a microwave reactor for a grafting reaction for 1.5h, control the microwave power to be 300W and the temperature to be 70℃, filter, wash the fiber with water and ethanol, then extract it with acetone in a Soxhlet extractor, dry it, and obtain allyl pentaerythritol grafted nylon fiber.

[0033] (2) Add 1.5L of dichloromethane and 50g of allyl pentaerythritol-grafted nylon fiber to a flask, stir, and then add 15g of triphenylchlorosilane, 6.8g of 4-dimethylaminopyridine and 6.3g of triethylamine. Stir and react at 20°C for 36h, filter, wash the fiber with dichloromethane and ethanol, and dry to obtain modified nylon fiber.

[0034] (3) Mix 500g of polyester polyol, 25g of modified nylon fiber, 32g of triethanolamine, 85g of dichlorofluoroethane, 28g of silicone oil, 6.4g of pentamethyldiethylenetriamine, 1.1g of dibutyltin dilaurate and 11g of water, then mix with 572g of polymethylene polyphenyl polyisocyanate, add to a mold, foam at 25°C, and then cure at 25°C for 36h to obtain wear-resistant and waterproof shoe sole material.

[0035] Example 3:

[0036] (1) Add 1L of 30mmol / L potassium persulfate aqueous solution and 40g of cleaned nylon fiber to a flask, place it in a microwave reactor for a pre-initiation reaction for 40min, control the microwave power to be 600W and the temperature to be 65℃; then add the fiber to 1L of 0.7mol / L allyloxypentaerythritol aqueous solution, place it in a microwave reactor for a grafting reaction for 2h, control the microwave power to be 600W and the temperature to be 65℃, filter, wash the fiber with water and ethanol, then extract it with acetone in a Soxhlet extractor, dry it, and obtain allyl pentaerythritol grafted nylon fiber.

[0037] (2) Add 1.5L of dichloromethane and 50g of allyl pentaerythritol-grafted nylon fiber to a flask, stir, and then add 9g of phenyldimethylchlorosilane, 4.4g of 4-dimethylaminopyridine and 4g of triethylamine. Stir and react at 30°C for 24h, filter, wash the fiber with dichloromethane and ethanol, and dry to obtain modified nylon fiber.

[0038] (3) Mix 500g polyester polyol, 40g modified nylon fiber, 26g 1,4-butanediol, 120g dichlorofluoroethane, 10g silicone oil, 12.6g triethylenediamine, 2.4g dibutyltin dilaurate, and 7g water. Then mix with 466g polymethylene polyphenyl polyisocyanate and 154g diphenylmethane diisocyanate. Add the mixture to a mold, foam at 20°C, and then cure at 70°C for 12 hours to obtain a wear-resistant and waterproof shoe sole material.

[0039] Comparative Example 1:

[0040] (1) Mix 500g polyester polyol, 27.5g 1,4-butanediol, 98g dichlorofluoroethane, 17g silicone oil, 11.3g triethylenediamine, 1.2g dibutyltin dilaurate and 10g water, then mix with 565g polymethylene polyphenyl polyisocyanate, add to a mold, foam at 30°C, and then cure at 40°C for 24 hours to obtain the sole material.

[0041] Comparative Example 2:

[0042] (1) Mix 500g polyester polyol, 10g nylon fiber, 27.5g 1,4-butanediol, 98g dichlorofluoroethane, 17g silicone oil, 11.3g triethylenediamine, 1.2g dibutyltin dilaurate and 10g water, then mix with 565g polymethylene polyphenyl polyisocyanate, add to a mold, foam at 30°C, and then cure at 40°C for 24 hours to obtain the sole material.

[0043] Comparative Example 3:

[0044] (1) Add 1L of potassium persulfate aqueous solution with a concentration of 15mmol / L and 40g of cleaned nylon fiber to a flask, place it in a microwave reactor for a pre-initiation reaction for 20min, control the microwave power to be 500W and the temperature to be 70℃; then add the fiber to 1L of vinyltrimethoxysilane aqueous solution with a concentration of 0.4mol / L, place it in a microwave reactor for a grafting reaction for 1h, control the microwave power to be 500W and the temperature to be 80℃, filter, wash the fiber with water and ethanol, then extract it with acetone in a Soxhlet extractor, dry it, and obtain vinyltrimethoxysilane grafted nylon fiber.

[0045] (2) Mix 500g polyester polyol, 10g vinyltrimethoxysilane grafted nylon fiber, 27.5g 1,4-butanediol, 98g dichlorofluoroethane, 17g silicone oil, 11.3g triethylenediamine, 1.2g dibutyltin dilaurate, and 10g water. Then mix with 565g polymethylene polyphenyl polyisocyanate, add to a mold, foam at 30°C, and then cure at 40°C for 24 hours to obtain wear-resistant and waterproof shoe sole material.

[0046] Comparative Example 4:

[0047] (1) Add 1L of potassium persulfate aqueous solution with a concentration of 15mmol / L and 40g of cleaned nylon fiber to a flask, place it in a microwave reactor for a pre-initiation reaction for 20min, control the microwave power to be 500W and the temperature to be 70℃; then add the fiber to 1L of allyl alcohol aqueous solution with a concentration of 0.4mol / L, place it in a microwave reactor for a grafting reaction for 1h, control the microwave power to be 500W and the temperature to be 80℃, filter, wash the fiber with water and ethanol, then extract it with acetone in a Soxhlet extractor, dry it, and obtain allyl alcohol grafted nylon fiber.

[0048] (2) Add 1L of dichloromethane and 50g of allyl alcohol-grafted nylon fiber to a flask, stir, add 3g of diphenylchlorosilane, 1.9g of 4-dimethylaminopyridine and 1.6g of triethylamine, stir and react at 25°C for 24h, filter, wash the fiber with dichloromethane and ethanol, dry, and obtain modified nylon fiber.

[0049] (3) Mix 500g polyester polyol, 10g modified nylon fiber, 27.5g 1,4-butanediol, 98g dichlorofluoroethane, 17g silicone oil, 11.3g triethylenediamine, 1.2g dibutyltin dilaurate and 10g water, then mix with 565g polymethylene polyphenyl polyisocyanate, add to a mold, foam at 30°C, and then cure at 40°C for 24 hours to obtain the sole material.

[0050] The abrasion resistance of the sole material was tested according to the method specified in GB / T 9867-2008 standard.

[0051] Tear strength was tested according to GB / T 10808-2006 standard.

[0052] The compressive strength was tested according to the method specified in GB / T 8813-2020 standard.

[0053] Dry the sole material and weigh it; then completely immerse it in water at 25℃ for 48 hours. After immersion, remove the sample, wipe off the surface moisture, weigh it, and calculate the water absorption rate W. W = (m - m0) / m0 × 100%. m0 is the mass of the sample before immersion, and m is the mass after immersion.

[0054] Table 1 Performance of shoe sole materials

[0055]

[0056] The polyurethane foam sole material in Comparative Example 1 has a relatively large volumetric abrasion, high water absorption, poor abrasion resistance and waterproof performance, and low tear strength and compressive strength, resulting in poor mechanical properties.

[0057] Modified nylon fibers were incorporated into the polyurethane foam sole materials of each embodiment. These nylon fibers possess strong abrasion resistance, and after grafting modification, numerous benzene ring structures were introduced onto the fiber surface. These structures form π-π bonds with the benzene rings in the polyurethane molecular chain, enhancing the interfacial force between the fiber and the polyurethane. This improves the abrasion resistance of the sole material, reduces relative volumetric abrasion loss, and improves the compatibility between the nylon fibers and the polyurethane matrix. The uniform dispersion of the nylon fibers within the foamed sole material significantly enhances the material's mechanical properties, notably increasing tear strength and compressive strength. Furthermore, the grafting of numerous hydrophobic siloxanes and benzene ring structures onto the nylon fiber surface forms a hydrophobic network within the sole material matrix, reducing water absorption and improving water resistance and waterproofing.

[0058] The interfacial forces between the nylon fibers and polyurethane added in Comparative Example 2 were low, resulting in poor compatibility and a relatively large volumetric abrasion of the sole material. The tear strength and compressive strength were low, and the abrasion resistance and mechanical properties were poor. Furthermore, the nylon fiber surface did not contain hydrophobic siloxanes and benzene ring structures, which was not conducive to reducing water absorption.

[0059] Compared to allyl pentaerythritol in Example 1, Comparative Example 3 uses conventional vinyltrimethoxysilane to graft nylon fibers. Vinyltrimethoxysilane has poor water solubility and poor grafting effect on nylon fibers. The modified fiber surface has less siloxane content and does not contain benzene ring structure. The interfacial force between nylon fibers and polyurethane is low, the compatibility is poor, the relative volumetric abrasion and water absorption of the sole material are large, and the tear strength and compressive strength are low.

[0060] Compared to allyl pentaerythritol in Example 1, Comparative Example 4 uses allyl alcohol to graft nylon fibers and reacts them with diphenylchlorosilane. The modified fiber surface has significantly less siloxane and benzene ring content than in Example 1. The sole material has a larger relative volumetric abrasion and water absorption rate, and lower tear strength and compressive strength.

[0061] The above description is merely a preferred embodiment of the present invention and is not intended to limit the present invention. Any modifications, equivalent substitutions, and improvements made within the spirit and principles of the present invention should be included within the protection scope of the present invention.

Claims

1. A wear-resistant and waterproof shoe sole material, characterized in that, The wear-resistant and waterproof shoe sole material comprises 100 parts by weight of polyester polyol, 2-8 parts by weight of modified nylon fiber, 5.2-6.4 parts by weight of chain extender, 17-24 parts by weight of foaming agent, 2-5.6 parts by weight of foam leveling agent, 1.5-3 parts by weight of catalyst, 1.4-2.2 parts by weight of water, and 113-124 parts by weight of isocyanate substance; The method for preparing the modified nylon fiber is as follows: (1) Add potassium persulfate aqueous solution and nylon fiber to a flask, place it in a microwave reactor for pre-initiation reaction, then add the fiber to an aqueous solution containing allyloxy pentaerythritol, place it in a microwave reactor for grafting reaction, filter, wash the fiber, then extract with acetone in a Soxhlet extractor, dry, and obtain allyl pentaerythritol grafted nylon fiber. (2) Add dichloromethane and allyl pentaerythritol-grafted nylon fibers to a flask, stir, add phenylchlorosilane compound, 4-dimethylaminopyridine and triethylamine, stir and react, filter, wash the fibers, dry, and obtain modified nylon fibers.

2. The wear-resistant and waterproof shoe sole material according to claim 1, characterized in that, The chain extender is any one or a combination of 1,4-butanediol and triethanolamine; the isocyanate is any one or a combination of polymethylene polyphenyl polyisocyanate and diphenylmethane diisocyanate.

3. The wear-resistant and waterproof shoe sole material according to claim 1, characterized in that, The catalyst is any one or a combination of triethylenediamine, pentamethyldiethylenetriamine, and dibutyltin dilaurate.

4. The wear-resistant and waterproof shoe sole material according to claim 1, characterized in that, The foaming agent is silicone oil; the foaming agent is dichlorofluoroethane.

5. The wear-resistant and waterproof shoe sole material according to claim 1, characterized in that, In (1), the concentration of potassium persulfate aqueous solution is 15-50 mmol / L; the concentration of allyloxypentaerythritol aqueous solution is 0.4-1 mol / L.

6. The wear-resistant and waterproof shoe sole material according to claim 1, characterized in that, In (1), the microwave power during the pre-initiation reaction is 300-600W, the temperature is 65-70℃, and the reaction time is 20-40min; the microwave power during the grafting reaction is 300-600W, the temperature is 65-80℃, and the reaction time is 1-2h.

7. The wear-resistant and waterproof shoe sole material according to claim 1, characterized in that, In (2), the mass ratio of allyl pentaerythritol-grafted nylon fiber, phenylchlorosilane compound, 4-dimethylaminopyridine, and triethylamine is 100:(6-30):(3.8-13.6):(3.2-12.6).

8. The wear-resistant and waterproof shoe sole material according to claim 7, characterized in that, The phenylchlorosilane compound is phenyldimethylchlorosilane, diphenylchlorosilane, or triphenylchlorosilane.

9. The wear-resistant and waterproof shoe sole material according to claim 1, characterized in that, In step (2), the reaction temperature is 20-30℃ and the reaction time is 24-36h.

10. A method for preparing a wear-resistant and waterproof shoe sole material as described in any one of claims 1-9, characterized in that, The preparation method is as follows: polyester polyol, modified nylon fiber, chain extender, foaming agent, foam leveling agent, catalyst, and water are stirred and mixed, then mixed with isocyanate, added to a mold, foamed at 20-40℃, and then cured at 25-70℃ for 12-36 hours to obtain wear-resistant and waterproof shoe sole material.

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