Polyurethane elastomer for low-temperature-resistant shoe material and preparation process of polyurethane elastomer

Abstract

The invention discloses a low-temperature-resistant polyurethane elastomer for shoe materials, which is prepared from the following raw materials in parts by weight: 40-50 parts of polypropylene oxide glycol, 30-35 parts of toluene diisocyanate, 5-7 parts of stannous octoate, 5-7 parts of 1, 4-butanediol, 3-4 parts of phosphite antioxidant, 2-3 parts of antioxidant, 3-4 parts of ultraviolet light absorber, 10-14 parts of modified fluoropolyether polyol and 12-14 parts of modified polysilsesquioxane. The invention relates to the technical field of polyurethane elastomers. According to the polyurethane elastomer for the low-temperature-resistant shoe material and the preparation process of the polyurethane elastomer, the structure of the polyurethane elastomer is changed from the molecular level through introduction and multiple modifications of the modified fluoropolyether polyol and the modified polysilsesquioxane. The modified substance can maintain the flexibility of a molecular chain at low temperature, the glass transition temperature of the material is reduced, the problems of hardening and embrittlement of a shoe sole under a cold condition are avoided, and normal use of the shoe in a low-temperature environment is guaranteed.

Description

Technical Field

[0001] The invention relates to the technical field of polyurethane elastomers, in particular to a polyurethane elastomer for low-temperature resistant shoe materials and a preparation process thereof. Background Art

[0002] Polyurethane elastomer is a polymer material with unique properties. The research on polyurethane elastomer began in the 1930s, when German scientist Otto Bayer first discovered the polymerization reaction of isocyanate and polyol, laying the foundation for the birth of polyurethane materials. At that time, the research focused on basic chemical principles and simple synthesis methods. With the increasing awareness of environmental protection and the increasingly stringent relevant regulations, the research focus of polyurethane elastomers has gradually shifted to the development of environmentally friendly materials. On the one hand, research and development of synthesis processes and raw materials with low volatile organic compound (VOC) emissions; on the other hand, efforts are made to improve the renewability and degradability of materials. At the same time, in order to meet the needs of high-end application fields such as aerospace, new energy, etc., the research and development of high-performance polyurethane elastomers has also made significant progress, such as the development of new polyurethane elastomer materials with higher heat resistance, fatigue resistance and chemical corrosion resistance.

[0003] Currently available polyurethane elastomers have limited high temperature resistance, poor waterproof and anti-corrosion effects, and insufficient chemical corrosion resistance, which limits their application in certain chemical environments. Summary of the invention

[0004] In view of the deficiencies in the prior art, the present invention provides a low-temperature resistant polyurethane elastomer for shoe materials and a preparation process thereof, which solves the problems in the above-mentioned background technology.

[0005] To achieve the above objectives, the present invention is implemented by the following technical scheme: A polyurethane elastomer for low-temperature resistant shoe materials, composed of the following raw materials in parts by weight: 40-50 parts of polypropylene oxide glycol, 30-35 parts of toluene diisocyanate, 5-7 parts of stannous octoate, 5-7 parts of 1,4-butanediol, 3-4 parts of phosphite antioxidant, 2-3 parts of antioxidant, 3-4 parts of ultraviolet absorber, 10-14 parts of modified fluoropolyether polyol and 12-14 parts of modified polysilsesquioxane;

[0006] The modified fluoropolyether polyol is composed of the following raw materials in parts by weight: 10-12 parts of fluoropolyether polyol, 9-11 parts of allyl glycidyl ether, 5-6 parts of benzoyl peroxide, 8-10 parts of diethanolamine and 9-13 parts of perfluorooctanoic acid;

[0007] The modified fluoropolyether polyol is prepared by the following steps:

[0008] A1, fluoropolyether polyol is slowly added into the reaction kettle, then the valve of the dropping funnel is opened and allyl glycidyl ether is slowly added dropwise;

[0009] A2. Close the reactor inlet and the dropping funnel valve, start the heating device, and raise the temperature in the reactor to 80°C at a heating rate of 2-3°C per minute;

[0010] A3. Under nitrogen protection, use a small spoon to quickly add the pre-weighed benzoyl peroxide powder into the reactor through a special feed port;

[0011] A4. After the temperature of the etherified fluoropolyether polyol in the reactor is lowered to 60°C, the valve of the dropping funnel is opened, and diethanolamine is slowly added dropwise. The dropping time is controlled within 10-15 minutes. After the dropping is completed, the temperature of the reactor is maintained at 60°C, the stirring speed is adjusted to 350 rpm, and the reaction is carried out for 2 hours;

[0012] A5. When the temperature of the reactor is controlled to reach 70°C, use a small spoon to quickly add the pre-weighed perfluorooctanoic acid into the reactor, maintain the temperature of the reactor at 70°C, adjust the stirring speed to 400 rpm, and react for 2.5 hours to obtain modified fluoropolyether polyol.

[0013] Preferably, the stirring speed is maintained at 100-150 rpm during the dropwise addition of A1.

[0014] Preferably, in the A2, during the heating process, the stirrer is turned on, the stirring speed is slowly adjusted to 300 rpm, and the stirring is continued for 30 minutes to fully mix the fluoropolyether polyol and the allyl glycidyl ether.

[0015] Preferably, after adding the materials to A3, the reaction is continued at 80° C. with a stirring speed of 300 rpm for 3 hours to obtain the etherified fluoropolyether polyol.

[0016] The modified polysilsesquioxane is prepared by the following steps:

[0017] B1. Slowly add octaaminophenyl to the reactor through the feed port, and then install a dropping funnel filled with glycidyl methacrylate on the feed port of the reactor; connect a nitrogen source to the gas inlet pipe, open the nitrogen valve, and completely replace the air in the reactor;

[0018] B2. While continuing to introduce nitrogen, use a dry spoon to quickly transfer dibutyltin dilaurate into the reactor, then close the feed port, start the stirrer, adjust the stirring speed to 300 rpm, and raise the temperature in the reactor to 90°C at a heating rate of 2-3°C per minute; introduce polymerizable double bonds into the polysilsesquioxane molecules through the reaction of amino groups and epoxy groups.

[0019] B3. Open the dropping funnel valve and slowly drop vinyl trimethoxysilane. The dropping time is controlled within 10-15 minutes to allow vinyl trimethoxysilane to be evenly added to the reaction system. After the dropping is completed, close the dropping funnel valve. Start the heating device and raise the temperature in the reactor to 70°C at a heating rate of 2-3°C per minute. Vinyl trimethoxysilane reacts with the double bonds on the polysilsesquioxane by addition reaction. At the same time, the hydrolysis condensation reaction of silane can form a cross-linked network on the surface of the polysilsesquioxane.

[0020] B4. Start the cooling device and lower the temperature in the reactor to 60°C at a cooling rate of 3-5°C per minute. During the cooling process, monitor the temperature in real time using a thermometer to ensure that the temperature accurately drops to 60°C. When the temperature reaches 60°C, use a small spoon to quickly add the pre-weighed p-phenylene diisocyanate into the reactor. The p-phenylene diisocyanate reacts with the remaining amino groups on the polysilsesquioxane to obtain a modified polysilsesquioxane.

[0021] Preferably, in B1, nitrogen is introduced into the reactor at a flow rate of 20-30 mL / min for 15-20 minutes.

[0022] Preferably, during the heating process in B2, the temperature change is closely monitored by a thermometer to ensure that the temperature is stable at 90° C. When the temperature reaches 90° C., the timing is started and the reaction lasts for 4 hours.

[0023] Preferably, in B3, when the temperature reaches 70° C., the stirring speed is adjusted to 350 rpm and the reaction is continued for 3 hours.

[0024] A preparation process of a polyurethane elastomer for low-temperature resistant shoe materials, comprising the following steps:

[0025] C1. Add the pretreated polyoxypropylene glycol, modified fluoropolyether polyol and modified polysilsesquioxane to a dry reaction kettle equipped with a stirrer, a thermometer, a condenser and a nitrogen inlet device, start the stirrer, set the stirring speed to 200-300 rpm, and preliminarily mix the materials in the kettle;

[0026] C2, slowly introduce dry nitrogen into the reactor at a flow rate of 10-20 mL / min for 15-20 minutes to exclude air from the reaction system, add toluene diisocyanate and stannous octoate under nitrogen protection, start the heating device, raise the temperature in the reactor to 70-75°C at a heating rate of 2-3°C per minute, react at this temperature for 2-3 hours, monitor the temperature in real time by a thermometer during the reaction, and keep the stirring speed at 300-400rpm;

[0027] C3, lower the temperature of the reactor to 90-100°C, slowly add dehydrated 1,4-butanediol, phosphite antioxidant and ultraviolet absorber, maintain the temperature at 90-100°C, stir at 300-400rpm, and react for 1.5-2 hours;

[0028] C4. The material in the reactor is degassed under a vacuum degree of -0.095 MPa or above for 15-30 minutes. During the degassed process, the material temperature is maintained at 80-90°C and the stirring speed is 100-200 rpm to remove bubbles generated during the reaction to obtain a low-temperature resistant polyurethane elastomer for shoe materials.

[0029] The present invention provides a polyurethane elastomer for low-temperature resistant shoe materials and a preparation process thereof. It has the following beneficial effects:

[0030] The introduction and multiple modifications of modified fluoropolyether polyols and modified polysilsesquioxanes have changed the structure of polyurethane elastomers at the molecular level. The modified substances can maintain the flexibility of the molecular chain at low temperatures, reduce the glass transition temperature of the material, avoid the problem of the sole becoming hard and brittle in cold conditions, and ensure the normal use of shoes in low temperature environments.

[0031] The elastic properties of the shoe are further optimized by adding modified polyurethane elastomer. The interaction between the molecular chains of the modified material and the special cross-linking structure allow the energy to be evenly dispersed and stored. When the pressure disappears, the molecular chains quickly return to their original state, releasing the stored energy, allowing the sole to quickly return to its original shape, providing continuous support and protection for the foot and reducing walking fatigue.

[0032] After three modifications, modified polysilsesquioxane can effectively improve the hardness and wear resistance of the material. The cross-linked structure and special nanoscale effect formed in the material enhance the material's load-bearing capacity, allowing the sole to better resist friction when in contact with the ground. DETAILED DESCRIPTION

[0033] The technical solutions in the embodiments of the present invention are described clearly and completely below. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of them. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0034] Embodiment 1

[0035] The present invention provides a technical solution: the modified fluoropolyether polyol is composed of the following raw materials in parts by weight: fluoropolyether polyol 10, allyl glycidyl ether 9, benzoyl peroxide 5, diethanolamine 8 and perfluorooctanoic acid 9;

[0036] The modified fluoropolyether polyol is prepared by the following steps:

[0037] A1, fluoropolyether polyol is slowly added into the reaction kettle, then the dropping funnel valve is opened, and allyl glycidyl ether is slowly added dropwise; during the addition, the stirring speed is maintained at 100-150rpm;

[0038] A2. Close the reactor feed port and the dropping funnel valve, start the heating device, and raise the temperature in the reactor to 80°C at a heating rate of 2-3°C per minute; during the heating process, turn on the agitator, slowly adjust the stirring speed to 300 rpm, and continue stirring for 30 minutes to fully mix the fluoropolyether polyol and allyl glycidyl ether;

[0039] A3. Under nitrogen protection, use a small spoon to quickly add the pre-weighed benzoyl peroxide powder into the reactor through a special feeding port; after adding, continue to react at 80°C with a stirring speed of 300 rpm for 3 hours to obtain etherified fluoropolyether polyol;

[0040] A4. After the temperature of the etherified fluoropolyether polyol in the reactor is lowered to 60°C, the valve of the dropping funnel is opened, and diethanolamine is slowly added dropwise. The dropping time is controlled within 10-15 minutes. After the dropping is completed, the temperature of the reactor is maintained at 60°C, the stirring speed is adjusted to 350 rpm, and the reaction is carried out for 2 hours;

[0041] A5. When the temperature of the reactor is controlled to reach 70°C, use a small spoon to quickly add the pre-weighed perfluorooctanoic acid into the reactor, maintain the temperature of the reactor at 70°C, adjust the stirring speed to 400 rpm, and react for 2.5 hours to obtain modified fluoropolyether polyol.

[0042] The modified polysilsesquioxane is prepared by the following steps:

[0043] B1. Slowly add octaaminophenyl to the reactor through the feed port, and then install a dropping funnel filled with glycidyl methacrylate on the feed port of the reactor; connect a nitrogen source to the gas inlet pipe, open the nitrogen valve, and completely replace the air in the reactor; introduce nitrogen into the reactor at a flow rate of 20-30 mL / min for 15-20 minutes;

[0044] B2. While continuing to introduce nitrogen, use a dry spoon to quickly transfer dibutyltin dilaurate to the reactor, then close the feed port, start the agitator, adjust the stirring speed to 300 rpm, and raise the temperature in the reactor to 90°C at a heating rate of 2-3°C per minute; during the heating process, closely monitor the temperature change with a thermometer to ensure that the temperature is stable at 90°C. When the temperature reaches 90°C, start the timing and the reaction lasts for 4 hours. Through the reaction of amino groups and epoxy groups, polymerizable double bonds are introduced into the polysilsesquioxane molecules.

[0045] B3. Open the dropping funnel valve and slowly drip vinyl trimethoxysilane. The dripping time is controlled within 10-15 minutes to allow vinyl trimethoxysilane to be evenly added to the reaction system. After the dripping is completed, close the dropping funnel valve. Start the heating device and raise the temperature in the reactor to 70°C at a heating rate of 2-3°C per minute. When the temperature reaches 70°C, adjust the stirring speed to 350rpm and continue the reaction for 3 hours. Vinyl trimethoxysilane reacts with the double bonds on the polysilsesquioxane by addition reaction. At the same time, the hydrolysis condensation reaction of silane can form a cross-linked network on the surface of the polysilsesquioxane.

[0046] B4. Start the cooling device and lower the temperature in the reactor to 60°C at a cooling rate of 3-5°C per minute. During the cooling process, monitor the temperature in real time using a thermometer to ensure that the temperature accurately drops to 60°C. When the temperature reaches 60°C, use a small spoon to quickly add the pre-weighed p-phenylene diisocyanate into the reactor. The p-phenylene diisocyanate reacts with the remaining amino groups on the polysilsesquioxane to obtain a modified polysilsesquioxane.

[0047] Embodiment 2

[0048] The present invention provides a technical solution: the modified fluoropolyether polyol is composed of the following raw materials in parts by weight: 11 fluoropolyether polyol, 10 allyl glycidyl ether, 5.5 benzoyl peroxide, 9 diethanolamine and 11 perfluorooctanoic acid;

[0049] The modified fluoropolyether polyol is prepared by the following steps:

[0050] A1, fluoropolyether polyol is slowly added into the reaction kettle, then the dropping funnel valve is opened, and allyl glycidyl ether is slowly added dropwise; during the addition, the stirring speed is maintained at 100-150rpm;

[0051] A2. Close the reactor feed port and the dropping funnel valve, start the heating device, and raise the temperature in the reactor to 80°C at a heating rate of 2-3°C per minute; during the heating process, turn on the agitator, slowly adjust the stirring speed to 300 rpm, and continue stirring for 30 minutes to fully mix the fluoropolyether polyol and allyl glycidyl ether;

[0052] A3. Under nitrogen protection, use a small spoon to quickly add the pre-weighed benzoyl peroxide powder into the reactor through a special feeding port; after adding, continue to react at 80°C with a stirring speed of 300 rpm for 3 hours to obtain etherified fluoropolyether polyol;

[0053] A4. After the temperature of the etherified fluoropolyether polyol in the reactor is lowered to 60°C, the valve of the dropping funnel is opened, and diethanolamine is slowly added dropwise. The dropping time is controlled within 10-15 minutes. After the dropping is completed, the temperature of the reactor is maintained at 60°C, the stirring speed is adjusted to 350 rpm, and the reaction is carried out for 2 hours;

[0054] A5. When the temperature of the reactor is controlled to reach 70°C, use a small spoon to quickly add the pre-weighed perfluorooctanoic acid into the reactor, maintain the temperature of the reactor at 70°C, adjust the stirring speed to 400 rpm, and react for 2.5 hours to obtain modified fluoropolyether polyol.

[0055] The modified polysilsesquioxane is prepared by the following steps:

[0056] B1. Slowly add octaaminophenyl to the reactor through the feed port, and then install a dropping funnel filled with glycidyl methacrylate on the feed port of the reactor; connect a nitrogen source to the gas inlet pipe, open the nitrogen valve, and completely replace the air in the reactor; introduce nitrogen into the reactor at a flow rate of 20-30 mL / min for 15-20 minutes;

[0057] B2. While continuing to introduce nitrogen, use a dry spoon to quickly transfer dibutyltin dilaurate to the reactor, then close the feed port, start the agitator, adjust the stirring speed to 300 rpm, and raise the temperature in the reactor to 90°C at a heating rate of 2-3°C per minute; during the heating process, closely monitor the temperature change with a thermometer to ensure that the temperature is stable at 90°C. When the temperature reaches 90°C, start the timing and the reaction lasts for 4 hours. Through the reaction of amino groups and epoxy groups, polymerizable double bonds are introduced into the polysilsesquioxane molecules.

[0058] B3. Open the dropping funnel valve and slowly drip vinyl trimethoxysilane. The dripping time is controlled within 10-15 minutes to allow vinyl trimethoxysilane to be evenly added to the reaction system. After the dripping is completed, close the dropping funnel valve. Start the heating device and raise the temperature in the reactor to 70°C at a heating rate of 2-3°C per minute. When the temperature reaches 70°C, adjust the stirring speed to 350rpm and continue the reaction for 3 hours. Vinyl trimethoxysilane reacts with the double bonds on the polysilsesquioxane by addition reaction. At the same time, the hydrolysis condensation reaction of silane can form a cross-linked network on the surface of the polysilsesquioxane.

[0059] B4. Start the cooling device and lower the temperature in the reactor to 60°C at a cooling rate of 3-5°C per minute. During the cooling process, monitor the temperature in real time using a thermometer to ensure that the temperature accurately drops to 60°C. When the temperature reaches 60°C, use a small spoon to quickly add the pre-weighed p-phenylene diisocyanate into the reactor. The p-phenylene diisocyanate reacts with the remaining amino groups on the polysilsesquioxane to obtain a modified polysilsesquioxane.

[0060] Embodiment 3

[0061] The present invention provides a technical solution: the modified fluoropolyether polyol is composed of the following raw materials in parts by weight: fluoropolyether polyol 12, allyl glycidyl ether 11, benzoyl peroxide 6, diethanolamine 10 and perfluorooctanoic acid 13;

[0062] The modified fluoropolyether polyol is prepared by the following steps:

[0063] A1, fluoropolyether polyol is slowly added into the reaction kettle, then the dropping funnel valve is opened, and allyl glycidyl ether is slowly added dropwise; during the addition, the stirring speed is maintained at 100-150rpm;

[0064] A2. Close the reactor feed port and the dropping funnel valve, start the heating device, and raise the temperature in the reactor to 80°C at a heating rate of 2-3°C per minute; during the heating process, turn on the agitator, slowly adjust the stirring speed to 300 rpm, and continue stirring for 30 minutes to fully mix the fluoropolyether polyol and allyl glycidyl ether;

[0065] A3. Under nitrogen protection, use a small spoon to quickly add the pre-weighed benzoyl peroxide powder into the reactor through a special feeding port; after adding, continue to react at 80°C with a stirring speed of 300 rpm for 3 hours to obtain etherified fluoropolyether polyol;

[0066] A4. After the temperature of the etherified fluoropolyether polyol in the reactor is lowered to 60°C, the valve of the dropping funnel is opened, and diethanolamine is slowly added dropwise. The dropping time is controlled within 10-15 minutes. After the dropping is completed, the temperature of the reactor is maintained at 60°C, the stirring speed is adjusted to 350 rpm, and the reaction is carried out for 2 hours;

[0067] A5. When the temperature of the reactor is controlled to reach 70°C, use a small spoon to quickly add the pre-weighed perfluorooctanoic acid into the reactor, maintain the temperature of the reactor at 70°C, adjust the stirring speed to 400 rpm, and react for 2.5 hours to obtain modified fluoropolyether polyol.

[0068] The modified polysilsesquioxane is prepared by the following steps:

[0069] B1. Slowly add octaaminophenyl to the reactor through the feed port, and then install a dropping funnel filled with glycidyl methacrylate on the feed port of the reactor; connect a nitrogen source to the gas inlet pipe, open the nitrogen valve, and completely replace the air in the reactor; introduce nitrogen into the reactor at a flow rate of 20-30 mL / min for 15-20 minutes;

[0070] B2. While continuing to introduce nitrogen, use a dry spoon to quickly transfer dibutyltin dilaurate to the reactor, then close the feed port, start the agitator, adjust the stirring speed to 300 rpm, and raise the temperature in the reactor to 90°C at a heating rate of 2-3°C per minute; during the heating process, closely monitor the temperature change with a thermometer to ensure that the temperature is stable at 90°C. When the temperature reaches 90°C, start the timing and the reaction lasts for 4 hours. Through the reaction of amino groups and epoxy groups, polymerizable double bonds are introduced into the polysilsesquioxane molecules.

[0071] B3. Open the dropping funnel valve and slowly drip vinyl trimethoxysilane. The dripping time is controlled within 10-15 minutes to allow vinyl trimethoxysilane to be evenly added to the reaction system. After the dripping is completed, close the dropping funnel valve. Start the heating device and raise the temperature in the reactor to 70°C at a heating rate of 2-3°C per minute. When the temperature reaches 70°C, adjust the stirring speed to 350rpm and continue the reaction for 3 hours. Vinyl trimethoxysilane reacts with the double bonds on the polysilsesquioxane by addition reaction. At the same time, the hydrolysis condensation reaction of silane can form a cross-linked network on the surface of the polysilsesquioxane.

[0072] B4. Start the cooling device and lower the temperature in the reactor to 60°C at a cooling rate of 3-5°C per minute. During the cooling process, monitor the temperature in real time using a thermometer to ensure that the temperature accurately drops to 60°C. When the temperature reaches 60°C, use a small spoon to quickly add the pre-weighed p-phenylene diisocyanate into the reactor. The p-phenylene diisocyanate reacts with the remaining amino groups on the polysilsesquioxane to obtain a modified polysilsesquioxane.

[0073] Embodiment 4

[0074] A polyurethane elastomer for low-temperature resistant shoe materials is composed of the following raw materials in parts by weight: 40 parts of polypropylene oxide glycol, 30 parts of toluene diisocyanate, 5 parts of stannous octoate, 5 parts of 1,4-butanediol, 3 parts of phosphite antioxidant, 2 parts of antioxidant, 3 parts of ultraviolet absorber, 10 parts of modified fluoropolyether polyol and 12 parts of modified polysilsesquioxane.

[0075] A preparation process of a polyurethane elastomer for low-temperature resistant shoe materials, comprising the following steps:

[0076] C1. Add the pretreated polyoxypropylene glycol, modified fluoropolyether polyol and modified polysilsesquioxane to a dry reaction kettle equipped with a stirrer, a thermometer, a condenser and a nitrogen inlet device, start the stirrer, set the stirring speed to 200-300 rpm, and preliminarily mix the materials in the kettle;

[0077] C2, slowly introduce dry nitrogen into the reactor at a flow rate of 10-20 mL / min for 15-20 minutes to exclude air from the reaction system, add toluene diisocyanate and stannous octoate under nitrogen protection, start the heating device, raise the temperature in the reactor to 70-75°C at a heating rate of 2-3°C per minute, react at this temperature for 2-3 hours, monitor the temperature in real time by a thermometer during the reaction, and keep the stirring speed at 300-400rpm;

[0078] C3, lower the temperature of the reactor to 90-100°C, slowly add dehydrated 1,4-butanediol, phosphite antioxidant and ultraviolet absorber, maintain the temperature at 90-100°C, stir at 300-400rpm, and react for 1.5-2 hours;

[0079] C4. The material in the reactor is degassed under a vacuum degree of -0.095 MPa or above for 15-30 minutes. During the degassed process, the material temperature is maintained at 80-90°C and the stirring speed is 100-200 rpm to remove bubbles generated during the reaction to obtain a low-temperature resistant polyurethane elastomer for shoe materials.

[0080] Embodiment 5

[0081] A polyurethane elastomer for low-temperature resistant shoe materials is composed of the following raw materials in parts by weight: 45 parts of polypropylene oxide glycol, 32 parts of toluene diisocyanate, 6 parts of stannous octoate, 6 parts of 1,4-butanediol, 3.5 parts of phosphite antioxidant, 2.5 parts of antioxidant, 3.5 parts of ultraviolet absorber, 12 parts of modified fluoropolyether polyol and 13 parts of modified polysilsesquioxane.

[0082] A preparation process of a polyurethane elastomer for low-temperature resistant shoe materials, comprising the following steps:

[0083] C1. Add the pretreated polyoxypropylene glycol, modified fluoropolyether polyol and modified polysilsesquioxane to a dry reaction kettle equipped with a stirrer, a thermometer, a condenser and a nitrogen inlet device, start the stirrer, set the stirring speed to 200-300 rpm, and preliminarily mix the materials in the kettle;

[0084] C2, slowly introduce dry nitrogen into the reactor at a flow rate of 10-20 mL / min for 15-20 minutes to exclude air from the reaction system, add toluene diisocyanate and stannous octoate under nitrogen protection, start the heating device, raise the temperature in the reactor to 70-75°C at a heating rate of 2-3°C per minute, react at this temperature for 2-3 hours, monitor the temperature in real time by a thermometer during the reaction, and keep the stirring speed at 300-400rpm;

[0085] C3, lower the temperature of the reactor to 90-100°C, slowly add dehydrated 1,4-butanediol, phosphite antioxidant and ultraviolet absorber, maintain the temperature at 90-100°C, stir at 300-400rpm, and react for 1.5-2 hours;

[0086] C4. The material in the reactor is degassed under a vacuum degree of -0.095 MPa or above for 15-30 minutes. During the degassed process, the material temperature is maintained at 80-90°C and the stirring speed is 100-200 rpm to remove bubbles generated during the reaction to obtain a low-temperature resistant polyurethane elastomer for shoe materials.

[0087] Embodiment 6

[0088] A polyurethane elastomer for low-temperature resistant shoe materials is composed of the following raw materials in parts by weight: 50 parts of polypropylene oxide glycol, 35 parts of toluene diisocyanate, 7 parts of stannous octoate, 7 parts of 1,4-butanediol, 4 parts of phosphite antioxidant, 3 parts of antioxidant, 4 parts of ultraviolet absorber, 14 parts of modified fluoropolyether polyol and 14 parts of modified polysilsesquioxane.

[0089] A preparation process of a polyurethane elastomer for low-temperature resistant shoe materials, comprising the following steps:

[0090] C1. Add the pretreated polyoxypropylene glycol, modified fluoropolyether polyol and modified polysilsesquioxane to a dry reaction kettle equipped with a stirrer, a thermometer, a condenser and a nitrogen inlet device, start the stirrer, set the stirring speed to 200-300 rpm, and preliminarily mix the materials in the kettle;

[0091] C2, slowly introduce dry nitrogen into the reactor at a flow rate of 10-20 mL / min for 15-20 minutes to exclude air from the reaction system, add toluene diisocyanate and stannous octoate under nitrogen protection, start the heating device, raise the temperature in the reactor to 70-75°C at a heating rate of 2-3°C per minute, react at this temperature for 2-3 hours, monitor the temperature in real time by a thermometer during the reaction, and keep the stirring speed at 300-400rpm;

[0092] C3, lower the temperature of the reactor to 90-100°C, slowly add dehydrated 1,4-butanediol, phosphite antioxidant and ultraviolet absorber, maintain the temperature at 90-100°C, stir at 300-400rpm, and react for 1.5-2 hours;

[0093] C4. The material in the reactor is degassed under a vacuum degree of -0.095 MPa or above for 15-30 minutes. During the degassed process, the material temperature is maintained at 80-90°C and the stirring speed is 100-200 rpm to remove bubbles generated during the reaction to obtain a low-temperature resistant polyurethane elastomer for shoe materials.

[0094] It should be noted that, in this article, relational terms such as first and second, etc. are only used to distinguish one entity or operation from another entity or operation, and do not necessarily require or imply any such actual relationship or order between these entities or operations. Moreover, the terms "include", "comprise" or any other variants thereof are intended to cover non-exclusive inclusion, so that a process, method, article or device including a series of elements includes not only those elements, but also other elements not explicitly listed, or also includes elements inherent to such process, method, article or device. In the absence of further restrictions. The sentence "includes an element defined by ... does not exclude the existence of other identical elements in the process, method, article or device including the element".

[0095] Although embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that various changes, modifications, substitutions and variations may be made to the embodiments without departing from the principles and spirit of the present invention, and that the scope of the present invention is defined by the appended claims and their equivalents.

Claims

1. A polyurethane elastomer for low temperature resistant shoe material, characterized in that: The invention is composed of the following raw materials in parts by weight: 40-50 parts of polyoxypropylene glycol, 30-35 parts of toluene diisocyanate, 5-7 parts of stannous octoate, 5-7 parts of 1,4-butanediol, 3-4 parts of phosphite antioxidant, 2-3 parts of antioxidant, 3-4 parts of ultraviolet absorber, 10-14 parts of modified fluoropolyether polyol and 12-14 parts of modified polysilsesquioxane; The modified fluoropolyether polyol is composed of the following raw materials in parts by weight: 10-12 parts of fluoropolyether polyol, 9-11 parts of allyl glycidyl ether, 5-6 parts of benzoyl peroxide, 8-10 parts of diethanolamine and 9-13 parts of perfluorooctanoic acid; The modified fluoropolyether polyol is prepared by the following steps: A1, fluoropolyether polyol is slowly added into the reaction kettle, then the valve of the dropping funnel is opened and allyl glycidyl ether is slowly added dropwise; A2. Close the reactor inlet and the dropping funnel valve, start the heating device, and raise the temperature in the reactor to 80°C at a heating rate of 2-3°C per minute; A3. Under nitrogen protection, use a small spoon to quickly add the pre-weighed benzoyl peroxide powder into the reactor through a special feed port; A4. After the temperature of the etherified fluoropolyether polyol in the reactor is lowered to 60°C, the valve of the dropping funnel is opened, and diethanolamine is slowly added dropwise. The dropping time is controlled within 10-15 minutes. After the dropping is completed, the temperature of the reactor is maintained at 60°C, the stirring speed is adjusted to 350 rpm, and the reaction is carried out for 2 hours; A5. When the temperature of the reactor is controlled to reach 70°C, use a small spoon to quickly add the pre-weighed perfluorooctanoic acid into the reactor, maintain the temperature of the reactor at 70°C, adjust the stirring speed to 400 rpm, and react for 2.5 hours to obtain modified fluoropolyether polyol.

2. The low-temperature resistant polyurethane elastomer for shoe materials according to claim 1, characterized in that: During the dropwise addition of A1, the stirring speed was maintained at 100-150 rpm.

3. The low-temperature resistant polyurethane elastomer for shoe materials according to claim 1, characterized in that: In the A2, during the heating process, the stirrer was turned on, the stirring speed was slowly adjusted to 300 rpm, and the stirring was continued for 30 minutes to fully mix the fluoropolyether polyol and the allyl glycidyl ether.

4. The low-temperature resistant polyurethane elastomer for shoe materials according to claim 1, characterized in that: After adding the materials to A3, the reaction was continued at 80° C. with a stirring speed of 300 rpm for 3 hours to obtain etherified fluoropolyether polyol.

5. The low-temperature resistant polyurethane elastomer for shoe materials according to claim 1, characterized in that: The modified polysilsesquioxane is prepared by the following steps: B1. Slowly add octaaminophenyl to the reactor through the feed port, and then install a dropping funnel filled with glycidyl methacrylate on the feed port of the reactor; connect a nitrogen source to the gas inlet pipe, open the nitrogen valve, and completely replace the air in the reactor; B2. While continuing to introduce nitrogen, use a dry spoon to quickly transfer dibutyltin dilaurate into the reactor, then close the feed port, start the stirrer, adjust the stirring speed to 300 rpm, and raise the temperature in the reactor to 90°C at a heating rate of 2-3°C per minute; introduce polymerizable double bonds into the polysilsesquioxane molecules through the reaction of amino groups and epoxy groups. B3. Open the dropping funnel valve and slowly drop vinyl trimethoxysilane. The dropping time is controlled within 10-15 minutes to allow vinyl trimethoxysilane to be evenly added to the reaction system. After the dropping is completed, close the dropping funnel valve. Start the heating device and raise the temperature in the reactor to 70°C at a heating rate of 2-3°C per minute. Vinyl trimethoxysilane reacts with the double bonds on the polysilsesquioxane by addition reaction. At the same time, the hydrolysis condensation reaction of silane can form a cross-linked network on the surface of the polysilsesquioxane. B4. Start the cooling device and lower the temperature in the reactor to 60°C at a cooling rate of 3-5°C per minute. During the cooling process, monitor the temperature in real time using a thermometer to ensure that the temperature accurately drops to 60°C. When the temperature reaches 60°C, use a small spoon to quickly add the pre-weighed p-phenylene diisocyanate into the reactor. The p-phenylene diisocyanate reacts with the remaining amino groups on the polysilsesquioxane to obtain a modified polysilsesquioxane.

6. The low-temperature resistant polyurethane elastomer for shoe materials according to claim 1, characterized in that: In the B1, nitrogen was introduced into the reactor at a flow rate of 20-30 mL / min for 15-20 minutes.

7. The low-temperature resistant polyurethane elastomer for shoe materials according to claim 1, characterized in that: During the heating process in B2, the temperature change was closely monitored by a thermometer to ensure that the temperature was stable at 90° C. When the temperature reached 90° C., the timing was started and the reaction lasted for 4 hours.

8. The low-temperature resistant polyurethane elastomer for shoe materials according to claim 1, characterized in that: In B3, when the temperature reaches 70° C., the stirring speed is adjusted to 350 rpm and the reaction is continued for 3 hours.

9. A process for preparing a polyurethane elastomer for low temperature resistant shoe material, characterized in that: It consists of the following steps: C1. Add the pretreated polyoxypropylene glycol, modified fluoropolyether polyol and modified polysilsesquioxane to a dry reaction kettle equipped with a stirrer, a thermometer, a condenser and a nitrogen inlet device, start the stirrer, set the stirring speed to 200-300 rpm, and preliminarily mix the materials in the kettle; C2, slowly introduce dry nitrogen into the reactor at a flow rate of 10-20 mL / min for 15-20 minutes to exclude air from the reaction system, add toluene diisocyanate and stannous octoate under nitrogen protection, start the heating device, raise the temperature in the reactor to 70-75°C at a heating rate of 2-3°C per minute, react at this temperature for 2-3 hours, monitor the temperature in real time by a thermometer during the reaction, and keep the stirring speed at 300-400rpm; C3, lower the temperature of the reactor to 90-100°C, slowly add dehydrated 1,4-butanediol, phosphite antioxidant and ultraviolet absorber, maintain the temperature at 90-100°C, stir at 300-400rpm, and react for 1.5-2 hours; C4. The material in the reactor is degassed under a vacuum degree of -0.095 MPa or above for 15-30 minutes. During the degassed process, the material temperature is maintained at 80-90°C and the stirring speed is 100-200 rpm to remove bubbles generated during the reaction to obtain a low-temperature resistant polyurethane elastomer for shoe materials.