Wear-resistant waterproof sole material and preparation method thereof

Abstract

The invention relates to the technical field of polyurethane soles, and discloses a wear-resistant waterproof sole material and a preparation method, the wear-resistant waterproof 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 a chain extender, 17-24 parts by weight of a foaming agent, 113-124 parts by weight of an isocyanate substance and the like; after the nylon fiber is subjected to graft modification, a large number of benzene ring structures are introduced to the surface of the fiber and form pi-pi bond interaction with benzene rings in a polyurethane molecular chain, so that the interfacial acting force between the fiber and polyurethane is improved, the wear resistance of a sole material is improved, the relative volume abrasion loss is reduced, and the tear strength and the compression strength are improved. A large number of hydrophobic siloxane and benzene ring structures are grafted on the surface of the nylon fiber, a hydrophobic network can be formed in a sole material matrix, the water absorption rate is reduced, and the water resistance and water resistance are improved.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of polyurethane soles, in particular to a wear-resistant and waterproof sole material and a preparation method thereof. BACKGROUND

[0002] Polyurethane foam has high elasticity, good shock resistance and pressure resistance, and excellent corrosion resistance, and is widely used in shoe materials, thermal insulation materials, building materials and the like. However, the mechanical strength of polyurethane foam is relatively low, and the wear resistance is not good, so it is difficult to obtain a shoe sole material with excellent performance. The use of polymer fibers, carbon fibers, nanoparticles and the like for reinforcing and modifying polyurethane foam can improve the mechanical strength, wear resistance and the like of polyurethane foam.

[0003] Nylon fibers have the advantages of high wear resistance, high modulus and high strength, and have important applications in high molecular materials such as foam plastics and rubbers. The Chinese patent with publication number CN112679941B discloses a high-strength soundproof polyurethane urea composite material, which adds polyurethane microspheres, nylon fibers, aramid fibers and the like reinforcing fibers to the polyurethane urea material, thereby improving the dispersibility and reinforcing effect of hollow inorganic fillers in the polyurethane urea composite material. However, the nylon fibers and the like of the patent do not reduce the water absorption of the polyurethane material, and do not improve the water resistance, which is not conducive to the practical application of the polyurethane material in shoe soles. SUMMARY

[0004] In view of the deficiencies of the prior art, the present application provides a wear-resistant and waterproof sole material and a preparation method thereof, which solves the problem of poor mechanical strength, wear resistance and the like of polyurethane shoe sole materials.

[0005] The technical solution of the present application is as follows: a wear-resistant and waterproof sole material and a preparation method thereof, the sole material comprising 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 stabilizer, 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 the wear-resistant and waterproof sole material is as follows: (1) adding a potassium persulfate aqueous solution and clean nylon fibers into a flask, and placing them in a microwave reactor for pre-initiation reaction, then adding the fibers into an aqueous solution containing allyloxy pentaerythritol, and placing them in a microwave reactor for grafting reaction, filtering, washing the fibers with water and ethanol, then extracting them with acetone in a Soxhlet extractor, and drying to obtain allyl pentaerythritol grafted nylon fibers.

[0007] (2) adding dichloromethane, allyl pentaerythritol grafted nylon fiber into the flask, stirring, then adding phenyl chlorosilane compound, 4-dimethylamino pyridine, triethylamine, stirring and reacting, then filtering, washing the fiber with dichloromethane and ethanol, drying, to obtain the modified nylon fiber.

[0008] (3) mixing polyester polyol, modified nylon fiber, chain extender, foaming agent, bubble uniformizing agent, catalyst, water, then mixing with isocyanate substance, adding into the mold, foaming at 20-40℃, then curing at 25-70℃ for 12-36h, to obtain the wear-resistant waterproof shoe sole material.

[0009] Preferably, the chain extender is any one or combination of 1,4-butanediol and triethanolamine.

[0010] Preferably, the isocyanate substance is any one or combination of polymethylene polyphenyl polyisocyanate and methylene diphenyl diisocyanate.

[0011] Preferably, the catalyst is any one or combination of triethylenediamine, pentamethyldiethylenetriamine and dibutyltin dilaurate.

[0012] Preferably, the bubble uniformizing agent is silicone oil.

[0013] Preferably, the foaming agent is monofluorodichloroethane.

[0014] Preferably, in (1), the concentration of potassium persulfate aqueous solution is 15-50mmol / L; the concentration of allyloxy pentaerythritol aqueous solution is 0.4-1mol / L.

[0015] 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.

[0016] Preferably, the microwave power during the grafting reaction is 300-600W, the temperature is 65-80℃, and the reaction time is 1-2h.

[0017] Preferably, in (2), the mass ratio of allyl pentaerythritol grafted nylon fiber, phenyl chlorosilane compound, 4-dimethylamino pyridine and triethylamine is 100:(6-30):(3.8-13.6):(3.2-12.6).

[0018] Preferably, in (2), the phenyl chlorosilane compound is phenyl dimethyl chlorosilane, diphenyl chlorosilane or triphenyl chlorosilane.

[0019] Preferably, in (2), the reaction temperature is 20-30℃, and the reaction time is 24-36h.

[0020] The application has the beneficial technical effects that: allyloxy pentaerythritol is used for microwave grafting reaction on the nylon fiber, a large number of hydroxyl groups are introduced on the surface of the nylon fiber, then the hydroxyl groups react with Si-Cl bonds of phenyl chlorosilane compounds, thereby a large number of siloxane and phenyl structures are introduced on the surface of the nylon fiber, and finally the nylon fiber, polyester polyol, foaming agent, catalyst, isocyanate substance and the like are blended and foamed to obtain a wear-resistant waterproof shoe sole material.

[0021] The nylon fiber in the application is modified by grafting, a large number of benzene ring structures are introduced on the surface of the fiber, π-π bond interaction is formed between the benzene ring structures and benzene rings in the polyurethane molecular chain, the interfacial force between the fiber and the polyurethane is improved, the wear resistance of the shoe sole material is improved, and the relative volume wear is reduced. Moreover, the compatibility of the nylon fiber and the polyurethane matrix is improved, the nylon fiber is uniformly dispersed in the foamed shoe sole material, the mechanical properties of the material are greatly improved, and the tear strength and compression strength are significantly improved.

[0022] The application grafts a large number of hydrophobic siloxane and benzene ring structures on the surface of the nylon fiber, a hydrophobic network can be formed in the matrix of the shoe sole material, the water absorption is reduced, and the water resistance and waterproof performance are improved. DETAILED DESCRIPTION

[0023] In order to make the technical problems, technical solutions and beneficial effects of the application clearer, the application is further described in detail below with reference to the embodiments. It should be understood that the specific embodiments described herein are only used to explain the application and not to limit the application.

[0024] The allyloxy pentaerythritol is prepared according to the method in the journal Chem. Commun., 2018, 54, 3875-3878, “In vivo drug tracking with 19F MRI at therapeutic dose”. 200 mL of water, 9.6 g of sodium hydroxide and 68 g of pentaerythritol are added to a flask, after stirring, 24.2 g of bromoallyl is added dropwise, heated to 70 DEG C, stirred for 8 h, 100 mL of water is added, extracted with ethyl acetate, the organic layer is distilled under reduced pressure, the crude product is separated by silica gel column chromatography, eluted with petroleum ether and ethyl acetate solution, to obtain allyloxy pentaerythritol, the structural formula is .

[0025] The following polyester polyol is YHY450C from Jining Fanghew Chemical Industry Co., Ltd. The nylon fiber is nylon 66 fiber with a length of 3 mm.

[0026] Example 1: (1) To a flask, 1 L of 15 mmol / L aqueous solution of potassium persulfate, 40 g of clean nylon fiber were added, and pre-irradiation was carried out in a microwave reactor for 20 min, with the microwave power controlled at 500 W and the temperature at 70°C; then the fiber was added to 1 L of 0.4 mol / L aqueous solution of allyloxy pentaerythritol, and grafting reaction was carried out in a microwave reactor for 1 h, with the microwave power controlled at 500 W and the temperature at 80°C; the fiber was filtered, washed with water and ethanol, then extracted with acetone in a Soxhlet extractor, and dried to obtain allyl pentaerythritol grafted nylon fiber.

[0027] (2) To a flask, 1.5 L of dichloromethane, 50 g of allyl pentaerythritol grafted nylon fiber were added, and after stirring, 15 g of triphenylchlorosilane, 6.8 g of 4-dimethylaminopyridine, 6.3 g of triethylamine were added, and stirring reaction was carried out at 20°C for 36 h; the fiber was filtered, washed with dichloromethane and ethanol, and dried to obtain modified nylon fiber.

[0028] (3) 500 g of polyester polyol, 10 g of modified nylon fiber, 27.5 g of 1,4-butanediol, 98 g of monofluorodichloroethane, 17 g of silicone oil, 11.3 g of triethylenediamine, 1.2 g of dibutyltin dilaurate, 10 g of water were stirred and mixed, and then mixed with 565 g of polymethylene polyphenyl polyisocyanate, and added to a mold, foamed and molded at 30°C, and then aged at 40°C for 24 h to obtain a wear-resistant waterproof shoe sole material.

[0029] Example 2: (1) To a flask, 1 L of 50 mmol / L aqueous solution of potassium persulfate, 40 g of clean nylon fiber were added, and pre-irradiation was carried out in a microwave reactor for 40 min, with the microwave power controlled at 300 W and the temperature at 70°C; then the fiber was added to 1 L of 1 mol / L aqueous solution of allyloxy pentaerythritol, and grafting reaction was carried out in a microwave reactor for 1.5 h, with the microwave power controlled at 300 W and the temperature at 70°C; the fiber was filtered, washed with water and ethanol, then extracted with acetone in a Soxhlet extractor, and dried to obtain allyl pentaerythritol grafted nylon fiber.

[0030] (2) To a flask, 1.5 L of dichloromethane, 50 g of allyl pentaerythritol grafted nylon fiber were added, and after stirring, 15 g of triphenylchlorosilane, 6.8 g of 4-dimethylaminopyridine, 6.3 g of triethylamine were added, and stirring reaction was carried out at 20°C for 36 h; the fiber was filtered, washed with dichloromethane and ethanol, and dried to obtain modified nylon fiber.

[0031] (3) 500 g polyester polyol, 25 g modified nylon fiber, 32 g triethanolamine, 85 g monofluorodichloroethane, 28 g silicone oil, 6.4 g pentamethyldiethylenetriamine, 1.1 g dibutyltin dilaurate, 11 g water were stirred and mixed, then mixed with 572 g polymethylene polyphenyl polyisocyanate, and added to a mold, foamed and formed at 25°C, then aged at 25°C for 36 h to obtain a wear-resistant waterproof shoe sole material.

[0032] Example 3: (1) A flask was added with 1 L of 30 mmol / L potassium persulfate aqueous solution, 40 g of clean nylon fiber, and placed in a microwave reactor for pre-initiation reaction for 40 min, with microwave power controlled at 600 W and temperature at 65°C; then the fiber was added to 1 L of 0.7 mol / L allyloxy pentaerythritol aqueous solution, and placed in a microwave reactor for grafting reaction for 2 h, with microwave power controlled at 600 W and temperature at 65°C, the fiber was filtered, washed with water and ethanol, then extracted with acetone in a Soxhlet extractor, and dried to obtain allyl pentaerythritol grafted nylon fiber.

[0033] (2) A flask was added with 1.5 L of dichloromethane, 50 g of allyl pentaerythritol grafted nylon fiber, stirred and then added with 9 g of phenyldimethylchlorosilane, 4.4 g of 4-dimethylaminopyridine, and 4 g of triethylamine, and stirred at 30°C for 24 h, the fiber was filtered, washed with dichloromethane and ethanol, and dried to obtain modified nylon fiber.

[0034] (3) 500 g polyester polyol, 40 g modified nylon fiber, 26 g 1,4-butanediol, 120 g monofluorodichloroethane, 10 g silicone oil, 12.6 g triethylenediamine, 2.4 g dibutyltin dilaurate, 7 g water were stirred and mixed, then mixed with 466 g polymethylene polyphenyl polyisocyanate and 154 g diphenylmethane diisocyanate, added to a mold, foamed and formed at 20°C, then aged at 70°C for 12 h to obtain a wear-resistant waterproof shoe sole material.

[0035] Comparative Example 1: (1) 500 g polyester polyol, 27.5 g 1,4-butanediol, 98 g monofluorodichloroethane, 17 g silicone oil, 11.3 g triethylenediamine, 1.2 g dibutyltin dilaurate, 10 g water were stirred and mixed, then mixed with 565 g polymethylene polyphenyl polyisocyanate, added to a mold, foamed and formed at 30°C, then aged at 40°C for 24 h to obtain a shoe sole material.

[0036] Comparative Example 2: (1) 500 g of polyester polyol, 10 g of nylon fiber, 27.5 g of 1,4-butanediol, 98 g of monofluorodichloroethane, 17 g of silicone oil, 11.3 g of triethylenediamine, 1.2 g of dibutyltin dilaurate, 10 g of water were stirred and mixed, and then mixed with 565 g of polymethylene polyphenyl polyisocyanate, and then added to a mold, foamed and molded at 30°C, and then cured at 40°C for 24 h to obtain a shoe sole material.

[0037] Comparative Example 3: (1) 1 L of an aqueous solution of potassium persulfate having a concentration of 15 mmol / L, 40 g of clean nylon fiber were added to a flask, and pre-initiation reaction was performed in a microwave reactor for 20 min, with the microwave power controlled at 500 W and the temperature at 70°C; then the fiber was added to 1 L of an aqueous solution of vinyltrimethoxysilane having a concentration of 0.4 mol / L, and grafting reaction was performed in a microwave reactor for 1 h, with the microwave power controlled at 500 W and the temperature at 80°C; the fiber was filtered, washed with water and ethanol, and then extracted with acetone in a Soxhlet extractor, and dried to obtain a vinyltrimethoxysilane grafted nylon fiber.

[0038] (2) 500 g of polyester polyol, 10 g of the vinyltrimethoxysilane grafted nylon fiber, 27.5 g of 1,4-butanediol, 98 g of monofluorodichloroethane, 17 g of silicone oil, 11.3 g of triethylenediamine, 1.2 g of dibutyltin dilaurate, 10 g of water were stirred and mixed, and then mixed with 565 g of polymethylene polyphenyl polyisocyanate, and then added to a mold, foamed and molded at 30°C, and then cured at 40°C for 24 h to obtain a wear-resistant waterproof shoe sole material.

[0039] Comparative Example 4: (1) 1 L of an aqueous solution of potassium persulfate having a concentration of 15 mmol / L, 40 g of clean nylon fiber were added to a flask, and pre-initiation reaction was performed in a microwave reactor for 20 min, with the microwave power controlled at 500 W and the temperature at 70°C; then the fiber was added to 1 L of an aqueous solution of allyl alcohol having a concentration of 0.4 mol / L, and grafting reaction was performed in a microwave reactor for 1 h, with the microwave power controlled at 500 W and the temperature at 80°C; the fiber was filtered, washed with water and ethanol, and then extracted with acetone in a Soxhlet extractor, and dried to obtain an allyl alcohol grafted nylon fiber.

[0040] (2) 1 L of dichloromethane, 50 g of the allyl alcohol grafted nylon fiber were added to a flask, and after stirring, 3 g of diphenylchlorosilane, 1.9 g of 4-dimethylaminopyridine, and 1.6 g of triethylamine were added, and stirring reaction was performed at 25°C for 24 h; the fiber was filtered, washed with dichloromethane and ethanol, and dried to obtain a modified nylon fiber.

[0041] (3) 500 g of polyester polyol, 10 g of modified nylon fiber, 27.5 g of 1,4-butanediol, 98 g of monofluorodichloroethane, 17 g of silicone oil, 11.3 g of triethylenediamine, 1.2 g of dibutyltin dilaurate, and 10 g of water were stirred and mixed, and then mixed with 565 g of polymethylene polyphenyl polyisocyanate, added to a mold, foamed at 30 ° C, and then aged at 40 ° C for 24 h to obtain a sole material.

[0042] The wear resistance of the sole material is tested according to the method specified in GB / T 9867-2008.

[0043] The tear strength is tested according to GB / T 10808-2006.

[0044] The compressive strength is tested according to the method specified in GB / T 8813-2020.

[0045] Dry the sole material and weigh it. Then completely immerse it in water at 25°C for 48 hours. After immersion, remove the sample, wipe off the surface moisture, and weigh it. 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.

[0046] Table 1 Properties of sole materials The polyurethane foam sole material of Comparative Example 1 has a large relative volume wear, high water absorption, poor wear resistance and waterproof performance, low tear strength and compression strength, and poor mechanical properties.

[0047] The polyurethane foam sole materials of each embodiment incorporate modified nylon fibers. The nylon fibers possess strong wear resistance. After grafting modification, numerous benzene ring structures are introduced onto the fiber surface, forming π-π bonds with the benzene rings in the polyurethane molecular chain. This enhances the interfacial forces between the fiber and the polyurethane, improving the wear resistance of the sole material and reducing relative volume wear. Furthermore, the nylon fibers improve their compatibility with the polyurethane matrix and are evenly dispersed within the foam sole material, significantly enhancing the mechanical properties of the material, significantly increasing its tear and compression strengths. 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.

[0048] The interfacial force between the nylon fiber added in Comparative Example 2 and the polyurethane is low and the compatibility is poor, resulting in a large relative volume wear of the sole material, low tear strength and compression strength, poor wear resistance and mechanical properties, and the nylon fiber surface does not contain hydrophobic silicone and benzene ring structure, which is not conducive to reducing water absorption.

[0049] Compared with the allyl pentaerythritol in Example 1, the Comparative Example 3 grafts the nylon fiber with conventional vinyl trimethoxysilane, the water solubility of the vinyl trimethoxysilane is poor, the grafting effect on the nylon fiber is poor, the siloxane content on the surface of the modified fiber is less, and the modified fiber does not contain benzene ring structure, the interfacial force between the nylon fiber and the polyurethane is low, the compatibility is poor, the relative volume abrasion and water absorption of the sole material are large, and the tear strength and compression strength are low.

[0050] Compared with the allyl pentaerythritol in Example 1, the Comparative Example 4 grafts the nylon fiber with allyl alcohol and reacts with diphenyl chlorosilane, the siloxane and benzene ring content on the surface of the modified fiber is significantly less than that in Example 1, the relative volume abrasion and water absorption of the sole material are large, and the tear strength and compression strength are low.

[0051] The above only describes the preferred embodiments of the present application and is not intended to limit the present application, and any modification, equivalent replacement and improvement made within the spirit and principle of the present application shall be included in the protection scope of the present application.

Claims

1. A wear-resistant and waterproof sole material, characterized in that: The wear-resistant and waterproof 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 preparation method of the modified nylon fiber is: (1) A potassium persulfate aqueous solution and nylon fibers are added to a flask, and the flask is placed in a microwave reactor for a pre-initiation reaction. The fibers are then added to an aqueous solution containing allyloxypentaerythritol, and the flask is placed in a microwave reactor for a grafting reaction. The fibers are filtered, washed, and then extracted with acetone in a Soxhlet extractor and dried to obtain allylpentaerythritol grafted nylon fibers. (2) Add dichloromethane and allyl pentaerythritol grafted nylon fiber into a flask, stir, then add phenylchlorosilane compound, 4-dimethylaminopyridine, and triethylamine, stir and react, filter, wash the fiber, and dry to obtain modified nylon fiber.

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

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

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

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

7. The wear-resistant and waterproof sole material according to claim 1, characterized in that: In the above (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 sole material according to claim 7, characterized in that: The phenylchlorosilane compound is phenyldimethylchlorosilane, diphenylchlorosilane or triphenylchlorosilane.

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

10. A method for preparing the wear-resistant and waterproof sole material according to any one of claims 1 to 9, characterized in that: The preparation method comprises the following steps: mixing polyester polyol, modified nylon fiber, chain extender, foaming agent, foam leveling agent, catalyst and water, then mixing with isocyanate, adding the mixture into a mold, foaming at 20-40° C., and then aging at 25-70° C. for 12-36 hours to obtain a wear-resistant and waterproof sole material.

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