Hydrolysis-resistant anti-skid polyurethane material and preparation method and application thereof

Abstract

The application discloses a hydrolysis-resistant antiskid polyurethane material and a preparation method and application thereof, and relates to the technical field of polyurethane materials. The hydrolysis-resistant antiskid polyurethane material disclosed by the application comprises the following components: A component, which is a polyester type acrylate polyol, an aromatic isocyanate and an organic tin catalyst; a B component, which is an epoxy group modified polyether polyol, triethylene tetramine, a nitrogen-containing catalyst, water, a foam stabilizer, TPE microparticles and modified wollastonite; and a C component, which is a hydroxyl-terminated polybutadiene; the modified wollastonite is prepared by modifying wollastonite with a polyacrylate oligomer. The hydrolysis-resistant antiskid polyurethane material provided by the application is prepared by using a semi-prepolymer method, the preparation process is easy to control, the processing performance is stable, the material has excellent mechanical strength, toughness and resilience, and the material has excellent hydrolysis resistance, high and low temperature resistance, wear resistance, antiskid property, aging resistance and other properties; the material can be used for a long time under harsh conditions such as humidity or low temperature, and the service life of the material when applied to a shoe sole material is improved.

Description

Technical Field

[0001] This invention belongs to the technical field of polyurethane materials, and particularly relates to a hydrolysis-resistant and slip-resistant polyurethane material, its preparation method, and its application in shoe soles. Background Technology

[0002] Polyurethane materials, due to their foamability, abrasion resistance, resilience, fatigue resistance, ease of processing, and bending resistance, have been widely used as high-performance shoe sole materials. With the continuous development of science and technology, to ensure the functionality and comfort of footwear products, shoe sole materials require low density and excellent properties such as hydrolysis resistance, oil resistance, high temperature resistance, aging resistance, high elasticity, bending resistance, impact resistance, abrasion resistance, and slip resistance, ensuring both performance and a long service life. Most polyurethane shoe sole materials on the market have a microporous structure, resulting in low density and high breathability. They not only possess excellent oil resistance, chemical resistance, flexural strength, and abrasion resistance, but also outstanding mechanical strength, shock absorption, and shape memory properties. However, conventional polyurethane sole materials generally have poor hydrolysis resistance and wet slip resistance. Moreover, in humid or low-temperature environments, their mechanical properties and elasticity are easily affected, resulting in decreased comfort, easy breakage of the sole, and reduced product lifespan. At the same time, after about a year of use, the microporous polyurethane material is prone to deformation, wear, and decreased slip resistance, which seriously affects the comfort and lifespan of the footwear.

[0003] Existing polyurethane materials mainly include polyester-based polyurethane, polyether-based polyurethane, and polycarbonate-based polyurethane. Polyester-based polyurethane, as a conventional shoe sole material, possesses excellent mechanical properties, resistance to thermal oxidation, high temperature resistance, and oil and solvent resistance. However, it is relatively expensive, prone to hydrolysis, and has poor low-temperature performance. Furthermore, while technicians have attempted to improve its hydrolysis resistance by introducing hydrolysis-resistant agents, these agents tend to migrate within the polyurethane material, affecting the stability of the sole material and shortening the product's lifespan. Polyether-based polyurethane exhibits excellent hydrolysis resistance, aging resistance, mildew resistance, low-temperature flexibility, and elasticity, and is relatively inexpensive. However, its mechanical properties are poor, its high-temperature resistance is weak, its resistance to polar solvents is poor, and its abrasion resistance and tear resistance are inferior to polyester-based polyurethane. Polycarbonate-type polyurethane contains carbonate bonds and ether bonds, combining the characteristics of both polyester-type and polyether-type polyurethane. It not only has high mechanical strength, wear resistance, oxidation resistance, and chemical corrosion resistance, but also excellent hydrolysis resistance. However, it has poor low-temperature flexibility, and the synthesis process of polycarbonate polyols is complex, costly, and difficult to process, which limits its large-scale application.

[0004] Invention patent CN202411949139.0 discloses a hydrophobic high-strength polyurethane flexible foam, comprising component A: vegetable oil modified polyester polyol, silane modified polyether polyol, silicone oil, catalyst, chain extender, and foaming agent; component B: polyether polyol 1, hydroxyl fluorosilicone oil, pure MDI, liquefied MDI, and polymerization inhibitor. It has excellent mechanical properties, hydrophobicity, anti-aging properties, elasticity, and wear resistance. However, the high and low temperature resistance and anti-slip performance of this polyurethane flexible foam are generally poor (mouse pads do not have requirements for these properties), and its mechanical strength also meets the requirements for shoe sole materials. Invention patent CN202210360539.2 discloses a polyurethane elastomer material, which is composed of polyester polyol and / or polyether polyol, isocyanate, foaming agent, chain extender, silicon nitride and modified montmorillonite. The modified montmorillonite is obtained by organic modification of ordinary montmorillonite with acrylamide, and it has excellent wear resistance. However, the polarity of polyester and polyether polyols is different, and their compatibility is poor, which affects the hydrolysis resistance, high and low temperature resistance and other properties of the polyurethane elastomer material, affecting its performance and service life, and failing to meet the functional requirements of existing shoe sole materials. Invention patent CN202411097938.X discloses a low-carbon polyurethane material for preparing foam shoe soles. It is made from bio-based polyols, bio-based isocyanates, and bio-based surfactants without the use of any heavy metal catalysts. This polyurethane material is biodegradable and has excellent mechanical properties, hydrolysis resistance, bending resistance, wear resistance, and flame retardancy. However, its macromolecular polyol is carbon dioxide-based polypropylene carbonate diol or / and bio-based diol. The preparation process is complex and the cost is extremely high, making it unsuitable for large-scale promotion and application. Summary of the Invention

[0005] The purpose of this invention is to provide a hydrolysis-resistant and slip-resistant polyurethane material, which is prepared by a semi-prepolymer method. The preparation process is easy to control, the processing performance is stable, and it has excellent mechanical strength, toughness and resilience. It has excellent hydrolysis resistance, high and low temperature resistance, wear resistance, slip resistance and aging resistance. It can be used for a long time in harsh conditions such as moisture or low temperature, thus improving its service life when applied to shoe sole materials.

[0006] To achieve the purpose of this invention, the present invention provides a hydrolysis-resistant and anti-slip polyurethane material made of component A, component B and component C. By mass percentage, the raw materials of component A are: 12-20 parts of polyester acrylate polyol, 70-90 parts of aromatic isocyanate and 0.1-0.16 parts of organotin catalyst. The raw materials for component B are: 15-25 parts of epoxy-modified polyether polyol, 7-10 parts of triethylenetetramine, 0.6-1.1 parts of nitrogen-containing catalyst, 0.07-0.5 parts of water, 0.5-1.5 parts of foam stabilizer, 5-10 parts of TPE microparticles, and 6-8 parts of modified wollastonite. The raw material for component C is: 12-30 parts of hydroxyl-terminated polybutadiene; The modified wollastonite is produced by modifying wollastonite with polyacrylate oligomers.

[0007] Furthermore, the polyester-type acrylate polyol is polycaprolactone-polyethylene glycol-acrylate with a molecular weight of 600-2000 and the following structural formula: .

[0008] Preferably, the polyester-type acrylate polyol of the present invention is selected from Qiyue Biotechnology.

[0009] The polyol selected in component A of this invention is polycaprolactone-polyethylene glycol-acrylate. The hydroxyl groups in its structure can react with isocyanate to obtain polyurethane prepolymer. At the same time, the polyol structure contains acrylate and polycaprolactone with terminal olefins, which makes it easy for free radical polymerization to occur during the reaction process of this invention, and thermal crosslinking to form a stable crosslinked network structure. This structure has excellent shape memory function, ensuring high resilience of the shoe sole material. It also improves the compatibility with the hard segments of polyurethane material, ensures its excellent resistance to low-temperature brittleness, and improves the hardness and mechanical properties of the material of this invention, and makes it have better weather resistance and aging resistance.

[0010] Furthermore, the aromatic isocyanate is polyether-modified MDI (preferably Wanhua's WANNATE). ® 6150E), carbamate-modified MDI (preferably Wanhua's WANNATE) ® 6170E), urethane-modified MDI (preferably Wanhua's WANNATE) ® Any one of 8310, 8609, 8617, and 8618. The preferred aromatic isocyanates of this invention are all polyether-modified MDI, which have lower costs, improve the elasticity and hydrolysis resistance of the polyurethane material of this invention, and ensure that this invention has good mechanical strength and high-temperature resistance.

[0011] Further, the preparation method of the epoxy-modified polyether polyol is as follows: trihydroxy polyoxypropylene ether is added to a 0.5 mol / L NaOH solution and stirred for 1-2 h, then epichlorohydrin and acetone are added, and the mixture is stirred and reacted at 50-60℃ for 3-5 h, followed by distillation and filtration to obtain a polyether polyol mixture; an appropriate amount of 10-15 wt% citric acid solution is added to the above polyether polyol mixture, and the mixture is sonicated for 0.5-1 h, followed by extraction, washing with deionized water, and distillation to obtain the epoxy-modified polyether polyol.

[0012] Furthermore, the ratio of the trihydroxy polyoxypropylene ether to the NaOH solution is 8-12 g / L; The ratio of epichlorohydrin to acetone is 0.8-1.5 g / mL; The amount of epichlorohydrin added is 2.0-3.5% of the mass of the trihydroxypolyoxypropylene ether.

[0013] The epoxy-modified polyether polyol of this invention is modified by introducing epoxy groups into the main chain or side chain of trihydroxy polyoxypropylene ether. This improves the compatibility between the polyether polyol and polyester-type acrylate polyols, TPE microparticles, and modified wollastonite, which is beneficial for the formation of cross-linked networks. This further enhances the mechanical strength, hardness, wear resistance, and high-temperature resistance of the polyurethane material, and it still exhibits superior anti-slip properties in low-temperature or humid environments. Moreover, when the polyurethane material suffers minor damage, the epoxy groups have a certain probability of repairing the micro-damage through dynamic bonds. If there are too many epoxy groups in the epoxy-modified polyether polyol, it will lead to a decrease in the number of hydroxyl groups in the polyether polyol, resulting in poor toughness and elasticity of the polyurethane material, easy breakage, and decreased anti-slip properties. If there are too few epoxy groups in the epoxy-modified polyether polyol, it will lead to a certain degree of decrease in the mechanical strength, water resistance, and other properties of the polyurethane material, and the anti-slip properties will be average. Therefore, this invention selects an epichlorohydrin addition amount of 2.0-3.5 wt% to achieve better overall performance of the polyurethane material.

[0014] Furthermore, the nitrogen-containing catalyst is bis(2-pyrrolidinylethyl) ether. Existing tertiary amine catalysts are volatile and environmentally harmful; the resulting polyurethane materials are easily oxidized and yellowed under high temperature or ultraviolet light; poor control of the tertiary amine dosage makes the processing difficult to control, leading to bubble rupture; residual tertiary amines also accelerate the hydrolysis of ester bonds, thereby reducing the service life of polyurethane materials. This invention uses bis(2-pyrrolidinylethyl) ether to replace tertiary amine catalysts, which can not only catalyze the foaming reaction of -NCO and H2O, but also cooperate with organotin catalysts to exert a synergistic effect, maintaining a good balance between foaming rate and gelation rate. During the foaming process, the polymer has sufficient strength to effectively encapsulate the gas, and after foaming, the polymer can solidify well, preventing the foam from shrinking or collapsing, resulting in a microporous elastomer with uniform pores and excellent overall performance.

[0015] Furthermore, the foam stabilizer is composed of sorbitan monooleate and polyether-modified polysiloxane in a mass ratio of 3:1. This invention uses an appropriate proportion of sorbitan monooleate and polyether-modified polysiloxane to increase the miscibility of the components, resulting in smaller, more uniform closed-cell bubbles. This stabilizes the cell structure and further improves the closed-cell rate and foam stabilization efficiency of the polyurethane material, thereby enhancing its hydrolysis resistance, compression resistance, and elasticity, and extending its service life.

[0016] Furthermore, the preparation method of the modified wollastonite is as follows: P1. Methyl methacrylate, butyl acrylate, azobisisobutyronitrile and mercaptoethanol are added to an appropriate amount of toluene and mixed evenly. Then, the mixture is added dropwise to a reactor under nitrogen protection. At the same time, the temperature is raised to 100-120℃ and the reaction is carried out for 4-6 hours. The impurities are removed by high-temperature distillation to obtain hydroxyl-terminated acrylate oligomers. P2. Then, the above-mentioned hydroxyl-terminated acrylate oligomer, liquefied MDI and dibutyltin dilaurate were added to an appropriate amount of toluene and dissolved. The mixture was then placed in a nitrogen-protected reactor and reacted at 70-75°C for 4-6 hours. After the reaction was completed, the toluene was removed by high-temperature distillation to obtain the polyacrylate oligomer. P3. Add wollastonite to an appropriate amount of acetone and stir until homogeneous to obtain a suspension. Then add the above polyacrylate oligomer to the suspension and stir at 70-80℃ for 1-2 hours. The filtered product is extracted with n-heptane and then dried at high temperature to obtain modified wollastonite.

[0017] Furthermore, the mass ratio of methyl methacrylate to butyl acrylate is 25:32; The amount of azobisisobutyronitrile added is 0.1-0.15% of the total mass of methyl methacrylate and butyl acrylate; The amount of mercaptoethanol added is 1.8-2.1% of the total mass of methyl methacrylate and butyl acrylate; The amount of liquefied MDI added is 20-30% of the mass of the terminal hydroxyl acrylate oligomer; preferably, the liquefied MDI is polyether-modified MDI; The amount of dibutyltin dilaurate added is 0.1-0.3% of the mass of the terminal hydroxyl acrylate oligomer; The amount of the polyacrylate oligomer added is 10-15% of the mass of the wollastonite.

[0018] The modified wollastonite of this invention is synthesized using methyl methacrylate and butyl acrylate as monomers and mercaptoethanol as a chain transfer agent to form a hydroxyl-terminated polyacrylate oligomer. This oligomer is then reacted with liquefied MDI to obtain an isocyanate-terminated polyacrylate oligomer. This isocyanate-terminated polyacrylate oligomer is then added to wollastonite for surface modification. The wollastonite added in this invention can be uniformly dispersed in component B and exhibits excellent interfacial bonding with other components of the polyurethane material. When used in conjunction with TPE microparticles, it significantly improves the mechanical strength, hardness, high-temperature resistance, wear resistance, and anti-slip properties of the polyurethane material. Simultaneously, it ensures that the invention possesses excellent resilience, bending resistance, and impact resistance, extending its service life. If conventional methods are used to modify wollastonite, such as using silane coupling agents, it is found that while improving the dispersion of wollastonite in component B increases the mechanical strength, hardness, and anti-slip properties of the polyurethane material, it reduces the resilience and impact resistance, affecting the comfort and durability of the shoe sole.

[0019] This invention also provides a method for preparing a hydrolysis-resistant and anti-slip polyurethane material, specifically including the following steps: S1. Weigh each raw material in component A, component B and component C according to the mass fraction, and dehydrate the polyester type acrylate polyol, epoxy modified polyether polyol and triethylenetetramine under vacuum at 100℃ for later use; S2. Add aromatic isocyanate to the reactor, heat to 50±5℃, then slowly add polyester-type acrylate polyol and organotin catalyst, while stirring and heating to 80±5℃, react for 2-3 hours, cool to 50℃ and simultaneously evacuate for 5 minutes to obtain polyurethane prepolymer, which is used as component A. S3. Add epoxy-modified polyether polyol, TPE microparticles and modified wollastonite to the above polyurethane prepolymer, stir at 50°C for 5-10 min, and add triethylenetetramine, nitrogen-containing catalyst, water and foam stabilizer at 50°C. Stir thoroughly and evenly to prepare component B for later use. S4. Add components A and B to the reactor and stir rapidly at 50°C for 5-10 minutes. Then add the hydroxyl-terminated polybutadiene of component C and continue stirring for 1-3 minutes to obtain the base material. Quickly pour the base material into a mold at 50°C and keep it warm for 5-10 minutes. Remove the mold and place it at 80°C for 12-24 hours to obtain a hydrolysis-resistant and anti-slip polyurethane material.

[0020] The hydrolysis-resistant and anti-slip polyurethane material provided by this invention, as well as the hydrolysis-resistant and anti-slip polyurethane material prepared by the above-described method, can be applied to shoe sole materials.

[0021] The present invention has achieved the following beneficial effects: 1. The polyurethane material of the present invention is prepared by a semi-prepolymer method. First, polyester-type acrylate polyol and excess aromatic isocyanate are reacted under the action of organotin catalyst to obtain polyurethane prepolymer. Then, epoxy-modified polyether polyol, triethylenetetramine, nitrogen-containing catalyst, water, foam stabilizer, TPE microparticles and modified wollastonite premixed component B are added and stirred evenly. Finally, hydroxyl-terminated polybutadiene is added as a capping agent to obtain the base material. The base material is cast in a mold, kept warm and cured to obtain the desired polyurethane material. This invention first uses polyols containing terminal olefins, acrylates, and polycaprolactone to prepolymerize with excess isocyanate, giving the polyurethane prepolymer high reactivity and forming a stable cross-linked network structure, thereby improving the mechanical strength, hardness, elasticity, and high and low temperature resistance of the invention. The subsequent addition of epoxy-modified polyether polyol allows the addition reaction to proceed while also inducing foaming, foam stabilization, and cross-linking reactions between the components. This process ensures uniform dispersion of the components and improves processing stability and process controllability. Triethylenetetramine is added as a chain extender, introducing double-bonded branches into the polyurethane material, facilitating reactions with the double bonds, hydroxyl groups, and isocyanates of components A and B, resulting in a stable cross-linked network structure. Furthermore, its use in conjunction with the nitrogen-containing catalyst of this invention balances the gelation and foaming rates during the polyurethane synthesis process, facilitating processing and improving the hardness, mechanical strength, and toughness of the polyurethane material. It also significantly enhances the wear resistance, hydrolysis resistance, high and low temperature resistance, and anti-slip properties of the polyurethane material of this invention.

[0022] 2. In this invention, polyester-type acrylate polyol and epoxy-modified polyether polyol are added separately, that is, the polyester-type acrylate polyol is prepolymerized first. This not only improves the compatibility between raw materials, but also makes the processing easier to control. The resulting polyurethane molecular chain segments are arranged regularly and the crosslinking network is stable, thereby improving the overall comprehensive performance of the polyurethane material of this invention. In particular, the hydrolysis resistance and anti-slip properties of this invention are outstanding.

[0023] 3. The polyurethane material of the present invention has high mechanical strength, high hardness and high elasticity, and also has excellent hydrolysis resistance, high temperature resistance, low temperature brittleness resistance, wear resistance, slip resistance, aging resistance, corrosion resistance and chemical resistance. It can be used for a long time under harsh conditions such as humidity or low temperature, which significantly improves the comfort and service life of shoe sole products.

[0024] 4. The raw materials selected in this invention are simple and readily available, with low cost, and the preparation process is easy to operate. It has excellent processing performance and high comprehensive performance, and can be used to produce shoe sole products using additive manufacturing technology. Detailed Implementation

[0025] The technical solutions in the embodiments of the present invention will be clearly and completely described below. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention.

[0026] The hydrolysis-resistant and anti-slip polyurethane material and its preparation method of the present invention will be described below with reference to specific embodiments.

[0027] In this embodiment of the invention, the polyester-type acrylate polyol is selected from Qiyue Biotechnology's polycaprolactone-polyethylene glycol-acrylate, with a molecular weight of 600-2000 and the structural formula as follows: ; Trihydroxy polyoxypropylene ether is selected from Haishihua's HSH-330 (hydroxyl value of 53-59 mgKOH / g) or HSH330N (hydroxyl value of 33-37 mgKOH / g). The nitrogen-containing catalyst was selected from bis(2-pyrrolidinylethyl) ether. The preparation method was as follows: 1.2 kg of pyrrolidin was added to a reaction vessel containing 267 g of 2-chloroethyl ether. At the same time, nitrogen gas was introduced into the reaction vessel and the temperature was raised to 70 °C. The reaction was carried out for 10 h. The product was purified by vacuum distillation to obtain bis(2-pyrrolidinylethyl) ether. The foam stabilizer is composed of sorbitan monooleate and polyether-modified polysiloxane (selected from Dayi Chemical's DY-ET200) in a mass ratio of 3:1. The TPE microparticles are selected from 500-mesh TPE powder from Four Leaf Plastics. The specification for wollastonite is 325 mesh; The hydroxyl-terminated polybutadiene was selected from NISSO-PB B-2000 of Nippon Soda. Other raw materials and reagents not mentioned in the embodiments of this invention are all commercially available.

[0028] It is worth noting that the polyester-type acrylate polyol, epoxy-modified polyether polyol, and triethylenetetramine mentioned in the embodiments of the present invention need to be vacuum dehydrated at 100°C before use.

[0029] Example 1 The preparation method of the hydrolysis-resistant and anti-slip polyurethane material in Example 1, based on parts by weight, is as follows: S1. Mix 70 parts of polyether-modified MDI (WANNATE from Wanhua). ®Add 6150E) to the reactor, heat to 50±5℃, then slowly add 12 parts of polyester-type acrylate polyol and 0.12 parts of dibutyltin dilaurate, while stirring and heating to 80±5℃, react for 3 hours, cool to 50℃ and simultaneously evacuate for 5 minutes to obtain polyurethane prepolymer, which is used as component A.

[0030] S2. Add 25 parts of epoxy-modified polyether polyol, 5 parts of TPE microparticles and 8 parts of modified wollastonite to the above polyurethane prepolymer, stir at 50°C for 10 min, and then add 7.2 parts of triethylenetetramine, 0.8 parts of nitrogen-containing catalyst, 0.11 parts of water and 0.5 parts of foam stabilizer at 50°C. Stir thoroughly and evenly to obtain component B for later use.

[0031] S3. Add components A and B to the reactor and stir rapidly at 50°C for 10 minutes. Then add 12.6 parts of terminal hydroxyl polybutadiene of component C and continue stirring for 3 minutes to obtain the base material. Then quickly pour the base material into a mold at 50°C and keep it warm for 5-10 minutes. Remove the mold and place it at 80°C for 12-24 hours to obtain a hydrolysis-resistant and anti-slip polyurethane material.

[0032] The preparation method of the above-mentioned epoxy-modified polyether polyol is as follows: 1 kg of trihydroxy polyoxypropylene ether (Hai Petrochemical's HSH-330N) is added to 100 mL of 0.5 mol / L NaOH solution and stirred for 1.5 h. Then, 20.1 g of epichlorohydrin and 20 mL of acetone are added, and the mixture is stirred and reacted at 60 °C for 4 h. After distillation and filtration, a polyether polyol mixture is obtained. 350 mL of 12 wt% citric acid solution is added to the above polyether polyol mixture, and the mixture is sonicated for 1 h. After extraction, washing with deionized water, and distillation, the epoxy-modified polyether polyol is obtained.

[0033] The preparation method of the above-mentioned wollastonite is as follows: P1. Add 500g of methyl methacrylate, 640g of butyl acrylate, 1.37g of azobisisobutyronitrile and 22.8g of mercaptoethanol to an appropriate amount of toluene and mix well. Then add the mixture dropwise to a reactor under nitrogen protection and heat it to 110℃. React for 5 hours and remove impurities by high-temperature distillation to obtain hydroxyl-terminated acrylate oligomers.

[0034] P2. Then, 500g of the above-mentioned hydroxyl-terminated acrylate oligomer and polyether-modified MDI (WANNATE from Wanhua) were added. ® 100g of 6150E and 0.5g of dibutyltin dilaurate were dissolved in 100mL of toluene, and then placed in a nitrogen-protected reactor and reacted at 70℃ for 6h. After the reaction was completed, the toluene was removed by high-temperature distillation to obtain polyacrylate oligomer.

[0035] P3. Add 1 kg of wollastonite to an appropriate amount of 200 mL of acetone and stir until homogeneous to obtain a suspension. Then add 150 g of the above polyacrylate oligomer to the suspension and stir at 70 °C for 2 h. The filtered product is extracted with n-heptane and then dried at high temperature to obtain modified wollastonite.

[0036] Example 2 The preparation method of the hydrolysis-resistant anti-slip polyurethane material in Example 2 is the same as that in Example 1, specifically referring to Example 1. The difference lies in the different mass ratios of components A, B, and C in the hydrolysis-resistant anti-slip polyurethane material of Example 2, as detailed below: The raw materials for component A are: 20 parts of polyester-type acrylate polyol, 90 parts of aromatic isocyanate, and 0.15 parts of organotin catalyst. The aromatic isocyanate is selected from urethane-modified MDI (preferably Wanhua's WANNATE). ® 6170E).

[0037] The raw materials for component B are: 18 parts of epoxy-modified polyether polyol, 9.8 parts of triethylenetetramine, 1.0 part of nitrogen-containing catalyst, 0.16 parts of water, 1.2 parts of foam stabilizer, 10 parts of TPE microparticles, and 6 parts of modified wollastonite.

[0038] The raw material for component C is 28.5 parts of hydroxyl-terminated polybutadiene.

[0039] The preparation method of the above-mentioned epoxy-modified polyether polyol is as follows: 1 kg of trihydroxy polyoxypropylene ether (Hai Petrochemical's HSH-330) is added to 100 mL of 0.5 mol / L NaOH solution and stirred for 1.5 h. Then, 30.8 g of epichlorohydrin and 30 mL of acetone are added, and the mixture is stirred and reacted at 60 °C for 4 h. After distillation and filtration, a polyether polyol mixture is obtained. 350 mL of 12 wt% citric acid solution is added to the above polyether polyol mixture, and the mixture is sonicated for 1 h. After extraction, washing with deionized water, and distillation, the epoxy-modified polyether polyol is obtained.

[0040] The preparation method of the above-mentioned wollastonite is as follows: P1. Add 500g of methyl methacrylate, 640g of butyl acrylate, 1.37g of azobisisobutyronitrile and 22.8g of mercaptoethanol to 200mL of toluene and mix well. Then add the mixture dropwise to a reactor under nitrogen protection and heat it to 110℃. React for 5h and remove impurities by high-temperature distillation to obtain hydroxyl-terminated acrylate oligomers.

[0041] P2. Then, 500g of the above-mentioned hydroxyl-terminated acrylate oligomer and polyether-modified MDI (WANNATE from Wanhua) were added. ®150g of 6150E and 1.5g of dibutyltin dilaurate were dissolved in 100mL of toluene, and then placed in a nitrogen-protected reactor and reacted at 70℃ for 6h. After the reaction was completed, the toluene was removed by high-temperature distillation to obtain polyacrylate oligomer.

[0042] P3. Add 1 kg of wollastonite to an appropriate amount of 200 mL of acetone and stir until homogeneous to obtain a suspension. Then add 100 g of the above polyacrylate oligomer to the suspension and stir at 70 °C for 2 h. The filtered product is extracted with n-heptane and then dried at high temperature to obtain modified wollastonite.

[0043] Example 3 The preparation method of the hydrolysis-resistant anti-slip polyurethane material in Example 3 is the same as that in Example 1, specifically referring to Example 1. The difference lies in the different mass ratios of components A, B, and C in the hydrolysis-resistant anti-slip polyurethane material of Example 3, as detailed below: The raw materials for component A are: 16 parts of polyester-type acrylate polyol, 76 parts of aromatic isocyanate, and 0.15 parts of organotin catalyst. The aromatic isocyanate is selected from urethane-modified MDI (preferably Wanhua's WANNATE). ® 8310).

[0044] The raw materials for component B are: 22.5 parts of epoxy-modified polyether polyol, 8.2 parts of triethylenetetramine, 0.9 parts of nitrogen-containing catalyst, 0.12 parts of water, 1.5 parts of foam stabilizer, 9 parts of TPE microparticles, and 8 parts of modified wollastonite.

[0045] The raw material for component C is 19.5 parts of hydroxyl-terminated polybutadiene.

[0046] The preparation method of the above-mentioned epoxy-modified polyether polyol is the same as that in Example 2, and the specific method is as described in Example 2.

[0047] The preparation method of the above-mentioned wollastonite is as follows: Step P1 is the same as in Example 2, please refer to Example 2 for details.

[0048] P2. Then, 500g of the above-mentioned hydroxyl-terminated acrylate oligomer and polyether-modified MDI (WANNATE from Wanhua) were added. ® 120g of 6150E and 0.9g of dibutyltin dilaurate were dissolved in 100mL of toluene, and then placed in a nitrogen-protected reactor and reacted at 70℃ for 6h. After the reaction was completed, the toluene was removed by high-temperature distillation to obtain polyacrylate oligomer.

[0049] P3. Add 1 kg of wollastonite to an appropriate amount of 200 mL of acetone and stir until homogeneous to obtain a suspension. Then add 120 g of the above polyacrylate oligomer to the suspension and stir at 70 °C for 2 h. The filtered product is extracted with n-heptane and then dried at high temperature to obtain modified wollastonite.

[0050] Example 4 The preparation method of the hydrolysis-resistant anti-slip polyurethane material in Example 4 is the same as that in Example 1, specifically referring to Example 1. The difference lies in the different mass ratios of components A, B, and C in the hydrolysis-resistant anti-slip polyurethane material of Example 4, as detailed below: The raw materials for component A are: 18 parts of polyester-type acrylate polyol, 85 parts of aromatic isocyanate, and 0.16 parts of organotin catalyst. The aromatic isocyanate is selected from polyether-modified MDI (preferably Wanhua's WANNATE). ® 6150E).

[0051] The raw materials for component B are: 20.8 parts of epoxy-modified polyether polyol, 8.9 parts of triethylenetetramine, 0.9 parts of nitrogen-containing catalyst, 0.15 parts of water, 1.2 parts of foam stabilizer, 8 parts of TPE microparticles, and 7 parts of modified wollastonite.

[0052] The raw material for component C is 22.4 parts of hydroxyl-terminated polybutadiene.

[0053] Comparative Example 1 The raw materials and preparation methods of the hydrolysis-resistant anti-slip polyurethane material in this comparative example are the same as those in Example 4, specifically referring to Example 4. The difference is that in this comparative example 1, the epoxy-modified polyether polyol is added to component A to prepare the polyurethane prepolymer; component B does not contain epoxy-modified polyether polyol.

[0054] Comparative Example 2 The raw materials and preparation methods of the hydrolysis-resistant anti-slip polyurethane material in this comparative example are the same as those in Example 4, specifically referring to Example 4. The difference is that castor oil-modified polyol (Sovermol 805) is used instead of polyester-type acrylate polyol in this comparative example 2, while the content remains unchanged.

[0055] Comparative Example 3 The raw materials and preparation methods of the hydrolysis-resistant anti-slip polyurethane material in this comparative example are the same as those in Example 4, specifically referring to Example 4. The difference is that castor oil-modified polyol (Sovermol 805) is used instead of epoxy-modified polyether polyol in this comparative example 3, while the content remains unchanged.

[0056] Comparative Example 4 The raw materials and preparation method of the hydrolysis-resistant anti-slip polyurethane material in this comparative example are the same as those in Example 4, specifically referring to Example 4. The difference is that the nitrogen-containing catalyst used in this comparative example 4 is triethylenediamine, with a content of 1.2 parts.

[0057] Comparative Example 5 The raw materials and preparation methods of the hydrolysis-resistant anti-slip polyurethane material in this comparative example are the same as those in Example 4, specifically referring to Example 4. The difference is that the amount of epichlorohydrin added to the epoxy-modified polyether polyol in this comparative example 5 is 1.5% of the mass of trihydroxypropylene ether.

[0058] Comparative Example 6 The raw materials and preparation methods of the hydrolysis-resistant anti-slip polyurethane material in this comparative example are the same as those in Example 4, specifically referring to Example 4. The difference is that the amount of epichlorohydrin added to the epoxy-modified polyether polyol in this comparative example 6 is 3.8% of the mass of trihydroxypropylene ether.

[0059] Comparative Example 7 The raw materials and preparation methods of the hydrolysis-resistant anti-slip polyurethane material in this comparative example are the same as those in Example 4, specifically referring to Example 4. The difference is that the modified wollastonite in this comparative example 7 is modified with a silane coupling agent, that is: by mass, 20 parts of wollastonite are added to 30 parts of acetone while stirring to obtain a suspension, and 5 parts of silane coupling agent KH-560 are added to the suspension while stirring to obtain a mixture. The mixture is heated to 90°C and stirred continuously for 60 minutes, and then filtered to obtain silane-modified wollastonite.

[0060] The mechanical properties, resilience, anti-slip properties, hydrolysis resistance, and low-temperature resistance of the hydrolysis-resistant and anti-slip polyurethane materials prepared in Examples 1-4 and Comparative Examples 1-7 were tested. The test results are shown in Tables 1 and 2 below.

[0061] Tensile strength: Tested according to the national standard GB / T6344-2008; Tear resistance: Tested according to the national standard GB / T10808-2006; Resilience: Tested according to the national standard GB / T1681-2009.

[0062] Anti-slip properties: Tested according to the national standard GB / T 3903.6-2005; Hydrolysis resistance: The retention rate (%) of mechanical properties was tested at hydrolysis temperature of 80℃, hydrolysis humidity of 95%, and hydrolysis time of 15 days and 30 days.

[0063] Table 1 Performance test results of hydrolysis-resistant and anti-slip polyurethane materials

[0064] Table 2 Performance test results of hydrolysis-resistant and anti-slip polyurethane materials

[0065] As can be seen from the test results in Tables 1 and 2 above, the hydrolysis-resistant and anti-slip polyurethane material of the present invention possesses excellent mechanical strength, resilience, hydrolysis resistance, anti-slip properties, flexural strength, and low-temperature resistance, ensuring the comfort and service life of the shoe sole. The combined use of the epoxy-modified polyether polyol and polyester-type acrylate polyol of the present invention significantly improves the mechanical strength, resilience, anti-slip properties, and hydrolysis resistance of the present invention.

[0066] The technical features of the above embodiments can be combined arbitrarily. For the sake of brevity, not all possible combinations of the technical features in the above embodiments are described. However, as long as there is no contradiction in the combination of these technical features, they should be considered to be within the scope of this specification.

[0067] The embodiments described above are merely examples of several implementations of the present invention, and while the descriptions are relatively specific and detailed, they should not be construed as limiting the scope of the present invention. It should be noted that those skilled in the art can make various modifications and improvements without departing from the concept of the present invention, and these modifications and improvements all fall within the scope of protection of the present invention.

Claims

1. A hydrolysis-resistant and anti-slip polyurethane material, made of component A, component B and component C, characterized in that, The raw materials of component A, by mass fraction, are: 12-20 parts of polyester-type acrylate polyol, 70-90 parts of aromatic isocyanate, and 0.1-0.16 parts of organotin catalyst; The raw materials for component B are: 15-25 parts of epoxy-modified polyether polyol, 7-10 parts of triethylenetetramine, 0.6-1.1 parts of nitrogen-containing catalyst, 0.07-0.5 parts of water, 0.5-1.5 parts of foam stabilizer, 5-10 parts of TPE microparticles, and 6-8 parts of modified wollastonite. The preparation method of the epoxy-modified polyether polyol is as follows: trihydroxy polyoxypropylene ether is added to a 0.5 mol / L NaOH solution and stirred for 1-2 h, then epichlorohydrin and acetone are added, and the mixture is stirred and reacted at 50-60℃ for 3-5 h. After distillation and filtration, a polyether polyol mixture is obtained. An appropriate amount of 10-15 wt% citric acid solution is added to the above polyether polyol mixture, and the mixture is sonicated for 0.5-1 h. After extraction, washing with deionized water, and distillation, the epoxy-modified polyether polyol is obtained. The amount of epichlorohydrin added is 2.0-3.5% of the mass of the trihydroxy polyoxypropylene ether; The nitrogen-containing catalyst is bis(2-pyrrolidinylethyl) ether; The raw material for component C is: 12-30 parts of hydroxyl-terminated polybutadiene; The modified wollastonite is prepared by modifying wollastonite with polyacrylate oligomers. The modified wollastonite is prepared by: P1. Methyl methacrylate, butyl acrylate, azobisisobutyronitrile and mercaptoethanol are added to an appropriate amount of toluene and mixed evenly. Then, the mixture is added dropwise to a reactor under nitrogen protection. At the same time, the temperature is raised to 100-120℃ and the reaction is carried out for 4-6 hours. The impurities are removed by high-temperature distillation to obtain hydroxyl-terminated acrylate oligomers. P2. Then, the above-mentioned hydroxyl-terminated acrylate oligomer, liquefied MDI and dibutyltin dilaurate were added to an appropriate amount of toluene and dissolved. The mixture was then placed in a nitrogen-protected reactor and reacted at 70-75°C for 4-6 hours. After the reaction was completed, the toluene was removed by high-temperature distillation to obtain the polyacrylate oligomer. P3. Add wollastonite to an appropriate amount of acetone and stir until homogeneous to obtain a suspension. Then add the above polyacrylate oligomer to the suspension and stir at 70-80℃ for 1-2 hours. The filtered product is extracted with n-heptane and then dried at high temperature to obtain modified wollastonite.

2. The hydrolysis-resistant and anti-slip polyurethane material according to claim 1, characterized in that, The polyester-type acrylate polyol is polycaprolactone-polyethylene glycol-acrylate, with a molecular weight of 600-2000, and its structural formula is: 。 3. The hydrolysis-resistant and anti-slip polyurethane material according to claim 1, characterized in that, The aromatic isocyanate is either polyether-modified MDI or urethane-modified MDI.

4. The hydrolysis-resistant and anti-slip polyurethane material according to claim 1, characterized in that, The ratio of the trihydroxy polyoxypropylene ether to the NaOH solution is 8-12 g / L; The ratio of epichlorohydrin to acetone is 0.8-1.5 g / mL.

5. The hydrolysis-resistant and anti-slip polyurethane material according to claim 1, characterized in that, The foam stabilizer is composed of sorbitan monooleate and polyether-modified polysiloxane in a mass ratio of 3:

1.

6. The hydrolysis-resistant and anti-slip polyurethane material according to claim 1, characterized in that, The mass ratio of methyl methacrylate to butyl acrylate is 25:32; The amount of azobisisobutyronitrile added is 0.1-0.15% of the total mass of methyl methacrylate and butyl acrylate; The amount of mercaptoethanol added is 1.8-2.1% of the total mass of methyl methacrylate and butyl acrylate; The amount of liquefied MDI added is 20-30% of the mass of the terminal hydroxyl acrylate oligomer, and the amount of dibutyltin dilaurate added is 0.1-0.3% of the mass of the terminal hydroxyl acrylate oligomer. The amount of the polyacrylate oligomer added is 10-15% of the mass of the wollastonite.

7. A method for preparing a hydrolysis-resistant and anti-slip polyurethane material as described in any one of claims 1-6, characterized in that, Specifically, the following steps are included: S1. Weigh each raw material in component A, component B and component C according to the mass fraction, and dehydrate the polyester type acrylate polyol, epoxy modified polyether polyol and triethylenetetramine under vacuum at 100℃ for later use; S2. Add aromatic isocyanate to the reactor, heat to 50±5℃, then slowly add polyester-type acrylate polyol and organotin catalyst, while stirring and heating to 80±5℃, react for 2-3 hours, cool to 50℃ and simultaneously evacuate for 5 minutes to obtain polyurethane prepolymer. S3. Add epoxy-modified polyether polyol, TPE microparticles and modified wollastonite to the above polyurethane prepolymer, stir at 50°C for 5-10 min, and add triethylenetetramine, nitrogen-containing catalyst, water and foam stabilizer at 50°C, stir thoroughly and evenly, and set aside for use. S4. Add the mixture obtained in step S3 to the reactor and stir rapidly at 50°C for 5-10 min. Then add hydroxyl-terminated polybutadiene and continue stirring for 1-3 min to obtain the base material. Then quickly pour the base material into a mold at 50°C and keep it warm for 5-10 min. Remove the mold and place it at 80°C for 12-24 h to obtain a hydrolysis-resistant and anti-slip polyurethane material.

8. The application of the hydrolysis-resistant and anti-slip polyurethane material as described in any one of claims 1-6, or the hydrolysis-resistant and anti-slip polyurethane material prepared by the preparation method described in claim 7, in shoe soles.

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