Temperature-resistant polyurethane sports protective materials, their preparation methods and applications

Abstract

This invention belongs to the technical field of polyurethane protective materials, specifically relating to a heat-resistant polyurethane sports protective material, its preparation method, and its application. It is composed of component A and component B in a mass ratio of 100:(50-65). Component A includes: polyether polyol 1, polyether polyol 2, polyether polyol 3, polymer polyol, chain extender, crosslinking agent, foaming agent, foam stabilizer, catalyst, and silane-modified nano-lignin; component B includes: polyether polyol 4, pure MDI, and liquefied MDI. The composite material of this invention possesses excellent physical properties, resistance to damp heat, and hydrophobic properties. Sports protective gear prepared using this material has the advantages of being lightweight, having high energy absorption, and being able to cope with complex and changing environmental conditions. This invention also provides its preparation method and application.

Description

Technical Field

[0001] This invention belongs to the technical field of polyurethane protective materials, specifically relating to a heat-resistant polyurethane sports protective material, its preparation method, and its application. Background Technology

[0002] In sports or scenarios with high safety requirements, such as motorcycling and skiing, protective materials must have impact protection design to provide reliable safety for high-risk sports; at the same time, protective materials must have characteristics such as high energy absorption, impact resistance and environmental adaptability.

[0003] Polyurethane slow-rebound materials possess unique viscoelasticity. Simultaneously, the open-cell structure within the material absorbs energy through molecular chain deformation upon impact, slowly returning to its original shape afterward, effectively reducing the risk of sports injuries. Experiments show that its energy absorption rate can reach over 90%, making it suitable for sports protective applications such as knee and elbow braces. However, in the face of complex and changing environmental conditions, conventional polyurethane materials are susceptible to erosion from factors such as humidity and temperature differences, leading to a decline in their protective performance.

[0004] Chinese patent CN114031741A discloses a high-performance polyurethane slow-rebound protective gear composite material and a method for preparing the protective gear. The composite material comprises the following raw materials by weight: 40-65 parts slow-rebound polyether polyol, 20-30 parts polymer polyol, 10-30 parts vegetable oil, 1-2 parts crosslinking agent, 1-5 parts chain extender, 0.2-0.6 parts foaming agent, 0.3-0.8 parts foam stabilizer, 1-3 parts catalyst, 1-3 parts cell opener, and 70-80 parts modified MDI. Protective gear made from this high-performance polyurethane slow-rebound protective gear composite material is resistant to high temperatures and hydrolysis, possesses excellent physical and mechanical properties, and exhibits high viscoelasticity near room temperature, which is beneficial for absorbing high impact energy and achieving good impact resistance. However, this patent is limited to room temperature environments and does not consider extreme environmental conditions, such as whether it can maintain impact resistance in hot or cold weather, or whether it retains its protective effect after long-term exposure to humid environments.

[0005] Therefore, it is particularly necessary to develop a new polyurethane slow rebound material to meet the current stringent requirements for hydrophobicity, low-temperature sensitivity, and high physical properties. Summary of the Invention

[0006] In view of the shortcomings of the prior art, the purpose of this invention is to provide a heat-resistant polyurethane sports protective material. This composite material has excellent physical properties, hydrophobic properties, and low-temperature sensitivity. Sports protective materials prepared using this material can effectively cope with complex and ever-changing environmental conditions.

[0007] Another objective of this invention is to provide a method for preparing and applying a heat-resistant polyurethane sports protective material.

[0008] The technical solution adopted in this invention is as follows:

[0009] The aforementioned heat-resistant polyurethane sports protective material is made of component A and component B in a mass ratio of 100:(50-65), wherein component A comprises the following raw materials in parts by mass:

[0010] Polyether polyol 1: 20-30 parts;

[0011] Polyether polyol 2: 20-40 parts;

[0012] Polyether polyol 3: 20-40 parts;

[0013] Polymer polyols: 10-20 parts;

[0014] Chain extender: 3-5 parts;

[0015] Crosslinking agent: 0.5-1 part;

[0016] Foaming agent: 0.3-0.6 parts;

[0017] Foam stabilizer: 0.4-0.8 parts;

[0018] Catalyst: 1-1.8 parts;

[0019] Modified silane: 10-20 parts;

[0020] Component B comprises the following parts by weight of raw materials:

[0021] Polyether polyol 4: 20-30 parts;

[0022] Pure MDI: 20-30 parts;

[0023] Liquefied MDI: 40-60 parts.

[0024] The polyether polyol 1 has a number average molecular weight of 2900-3100, a functionality of 3, and a hydroxyl value of 54.5-57.5 mgKOH / g; preferably, it is INOVOL C3050A from Shandong Yinuowei New Materials Co., Ltd.

[0025] The polyether polyol 2 has a number average molecular weight of 660-750, a functionality of 3, and a hydroxyl value of 225-255 mgKOH / g; preferably, it is INOVOL C307 from Shandong Yinuowei New Materials Co., Ltd.

[0026] The polyether polyol 3 has a number average molecular weight of 1530-1600, a functionality of 3, and a hydroxyl value of 105.0-110.0 mgKOH / g; preferably CHE-5107VE from Changhua Chemical Technology Co., Ltd.

[0027] The polyether polyol 4 has a number average molecular weight of 1000-4000, a functionality of 2, and a hydroxyl value of 28-112 mgKOH / g; preferably, it is one of INOVOL C210, INOVOL C220, INOVOL C230 or INOVOLC240A from Shandong Yinuowei New Materials Co., Ltd.

[0028] The modified silane is silane-modified nano-lignin.

[0029] The polymer polyol has a functionality of 3, a hydroxyl value of 19.0-23.0 mgKOH / g, and a solid content of 41.0-45.0%, preferably CHP-H45D from Changhua Chemical Technology Co., Ltd.

[0030] The chain extender is one or both of ethylene glycol and 1,4-butanediol.

[0031] The crosslinking agent is one or both of diethanolamine or triethanolamine.

[0032] The foaming agent is water.

[0033] The foam stabilizer is an organosilicon foam stabilizer, preferably UA-8823LV from Hemu New Material Technology (Shanghai) Co., Ltd.

[0034] The catalyst is A33, preferably DXCAT. ® A33.

[0035] The method for preparing silane-modified nano-lignin includes the following steps:

[0036] 1) A 30-50% NaOH solution with a mass ratio of (15-20):1 is reacted with 400-600 mesh corn stalk powder at 45-50℃ for 1-1.5h, followed by filtration and drying. The dried powder is then hydrolyzed with a 25-35% NaOH solution at a mass ratio of 1:(20-25) at 175-185℃ for 5.5-6.5h. After centrifugation and washing, the powder is dispersed in ethanol, and then homogenized under high pressure (1000-2000 bar) and freeze-dried to obtain nano-lignin.

[0037] 2) Nano-lignin, K2CO3 and tert-butyldimethylsilane in a mass ratio of (10-15):(0.2-0.25):(0.4-0.5) are dissolved in DMSO and reacted at 130-140℃ for 4-6 h to obtain silane-modified lignin;

[0038] 3) The silane-modified lignin is dispersed in ethanol, and then subjected to ultrasonic treatment (250W, 10min) and freeze-drying to obtain silane-modified nano-lignin.

[0039] The preparation method of the heat-resistant polyurethane sports protective material of the present invention includes the following steps:

[0040] (1) Preparation of component A: Polyether polyol 1, polyether polyol 2, polyether polyol 3, polymer polyol, chain extender, crosslinking agent, foaming agent, foam stabilizer, catalyst and modified silane are added into the reactor, heated to 40-50℃, stirred at 35-40r / min for 40-50min to obtain component A;

[0041] (2) Preparation of component B: Polyether polyol 4, pure MDI and liquefied MDI are stirred at 80-85℃ and 30-35 r / min for 80-90 min to obtain component B;

[0042] (3) Mix components A and B evenly according to the mass ratio, inject into the mold, open the mold and cure after 4-5 minutes to obtain heat-resistant polyurethane sports protective material.

[0043] The heat-resistant polyurethane sports protective material described in this invention is used in sports protective gear materials.

[0044] Compared with the prior art, the beneficial effects of the present invention are as follows:

[0045] (1) The present invention uses biomass raw materials to synthesize a highly efficient hydrophobic additive, which broadens the path of biomass resource utilization, endows the product with high hydrophobic properties, and enables the final heat-resistant polyurethane sports protective material to maintain long-term stability in a humid environment.

[0046] (2) Through formulation design, this invention introduces low-temperature sensitive polyether into the system, which significantly improves the hardness of the product at low temperatures, enabling it to maintain stable performance in environments ranging from -10℃ to 40℃. These performance improvements make the polyurethane composition of this invention particularly suitable for materials such as sports protective gear;

[0047] (3) The preparation method of the present invention can stably produce products with excellent performance by precisely controlling the ratio of component A and component B and the preparation conditions. It is simple to operate and easy to industrialize. Detailed Implementation

[0048] The present invention will be further described below with reference to the embodiments, but these embodiments do not limit the implementation of the present invention.

[0049] Unless otherwise specified, the raw materials used in the examples and comparative examples are all commercially available materials, and the process methods used in the examples and comparative examples are all conventional methods in the art.

[0050] The following is a description of some of the raw materials used in the examples and comparative examples:

[0051] CHE-5107VE and CHP-H45D were purchased from Changhua Chemical Technology Co., Ltd.

[0052] INOVOL C3050A, INOVOL C307, INOVOL C210, INOVOL C220, INOVOL C230, and INOVOL C240A: purchased from Shandong Yinuowei New Materials Co., Ltd.

[0053] DXCAT ® A33: Purchased from Shandong Dingxin New Material Technology Co., Ltd.;

[0054] UA-8823LV: Purchased from Hemu New Materials Technology (Shanghai) Co., Ltd.

[0055] Example 1

[0056] The aforementioned heat-resistant polyurethane sports protective material is made of component A and component B in a mass ratio of 100:55, wherein component A comprises the following raw materials in parts by mass:

[0057] INOVOL C3050A: 20 copies;

[0058] INOVOL C307: 20 copies;

[0059] CHE-5107VE: 40 servings;

[0060] CHP-H45D: 20 servings;

[0061] Ethylene glycol: 3 parts;

[0062] Diethanolamine: 0.5 parts;

[0063] UA-8823LV: 0.4 parts;

[0064] DXCAT ® A33: 1 copy;

[0065] Water: 0.3 parts;

[0066] Silane-modified nano-lignin: 10 parts;

[0067] Component B comprises the following parts by weight of raw materials:

[0068] INOVOL C210: 20 copies;

[0069] Pure MDI: 20 parts;

[0070] Liquefied MDI: 60 parts.

[0071] The method for preparing silane-modified nano-lignin includes the following steps:

[0072] 1) A 30% NaOH solution with a mass ratio of 15:1 was reacted with 400-mesh corn stalk powder at 45℃ for 1 hour, followed by filtration and drying. The dried powder was then hydrolyzed with a 25% NaOH solution at a mass ratio of 1:20 at 175℃ for 5.5 hours. After centrifugation and washing, the powder was dispersed in ethanol, then homogenized under high pressure (1000 bar) and freeze-dried to obtain nano-lignin.

[0073] 2) Nano-lignin, K2CO3 and tert-butyldimethylsilane in a mass ratio of 10:0.2:0.4 were dissolved in DMSO and reacted at 130℃ for 4 h to obtain silane-modified lignin;

[0074] 3) The silane-modified lignin is dispersed in ethanol, and then subjected to ultrasonic treatment (250W, 10min) and freeze-drying to obtain silane-modified nano-lignin.

[0075] The preparation method of the heat-resistant polyurethane sports protective material includes the following steps:

[0076] (1) Preparation of component A: INOVOL C3050A, INOVOL C307, CHE-5107VE, CHP-H45D, ethylene glycol, diethanolamine, UA-8823LV, and DXCAT were prepared. ® A33, water and silane-modified nano-lignin were added to the reactor, heated to 40°C, stirred at 35 r / min for 40 min to obtain component A;

[0077] (2) Preparation of component B: INOVOL C210, pure MDI and liquefied MDI were stirred at 80℃ for 80 min at a speed of 30 r / min to obtain component B, which had an -NCO content of 22.66%;

[0078] (3) Mix component A and component B at a mass ratio of 100:55 evenly, inject into the mold, open the mold and cure after 4 minutes to obtain a heat-resistant polyurethane sports protective material.

[0079] Example 2

[0080] The aforementioned heat-resistant polyurethane sports protective material is made of component A and component B in a mass ratio of 100:50, wherein component A comprises the following raw materials in parts by mass:

[0081] INOVOL C3050A: 20 copies;

[0082] INOVOL C307: 30 copies;

[0083] CHE-5107VE: 30 servings;

[0084] CHP-H45D: 20 servings;

[0085] 1,4-Butanediol: 4 parts;

[0086] Triethanolamine: 0.8 parts;

[0087] UA-8823LV: 0.4 parts;

[0088] DXCAT ® A33: 1.2 copies;

[0089] Water: 0.4 parts;

[0090] Silane-modified nano-lignin: 12 parts;

[0091] Component B comprises the following parts by weight of raw materials:

[0092] INOVOL C220: 25 servings;

[0093] Pure MDI: 30 parts;

[0094] Liquefied MDI: 45 parts.

[0095] The method for preparing silane-modified nano-lignin includes the following steps:

[0096] 1) A 40% NaOH solution with a mass ratio of 16:1 was reacted with 500-mesh corn stalk powder at 47.5℃ for 1.2h, followed by filtration and drying. The dried powder was then hydrolyzed with a 30% NaOH solution at a mass ratio of 1:22 at 175℃ for 5.5h. After centrifugation and washing, the powder was dispersed in ethanol, then homogenized under high pressure (2000 bar) and freeze-dried to obtain nano-lignin.

[0097] 2) Nano-lignin, K2CO3 and tert-butyldimethylsilane in a mass ratio of 10:0.2:0.4 were dissolved in DMSO and reacted at 130℃ for 5 h to obtain silane-modified lignin;

[0098] 3) The silane-modified lignin is dispersed in ethanol, and then subjected to ultrasonic treatment (250W, 10min) and freeze-drying to obtain silane-modified nano-lignin.

[0099] The preparation method of the heat-resistant polyurethane sports protective material includes the following steps:

[0100] (1) Preparation of component A: INOVOL C3050A, INOVOL C307, CHE-5107VE, CHP-H45D, 1,4-butanediol, triethanolamine, UA-8823LV, and DXCAT were prepared. ® A33, water, and silane-modified nano-lignin were added to a reaction vessel, heated to 45°C, stirred at a speed of 37.5 r / min for 45 min, and component A was obtained.

[0101] (2) Preparation of component B: INOVOL C220, pure MDI and liquefied MDI were stirred at 82.5℃ for 85 min at a speed of 32.5 r / min to obtain component B, which has an -NCO content of 22.25%;

[0102] (3) Mix component A and component B at a mass ratio of 100:50, inject into the mold, open the mold and cure after 4.5 min to obtain a heat-resistant polyurethane sports protective material.

[0103] Example 3

[0104] The aforementioned heat-resistant polyurethane sports protective material is made of component A and component B in a mass ratio of 100:65, wherein component A comprises the following raw materials in parts by mass:

[0105] INOVOL C3050A: 30 servings;

[0106] INOVOL C307: 20 copies;

[0107] CHE-5107VE: 40 servings;

[0108] CHP-H45D: 10 servings;

[0109] Ethylene glycol: 5 parts;

[0110] Diethanolamine: 0.5 parts;

[0111] Triethanolamine: 0.5 parts;

[0112] UA-8823LV: 0.5 copies;

[0113] DXCAT ® A33: 1.4 copies;

[0114] Water: 0.5 parts;

[0115] Silane-modified nano-lignin: 16 parts;

[0116] Component B comprises the following parts by weight of raw materials:

[0117] INOVOL C230: 30 servings;

[0118] Pure MDI: 30 parts;

[0119] Liquefied MDI: 40 parts.

[0120] The method for preparing silane-modified nano-lignin includes the following steps:

[0121] 1) A 50% NaOH solution with a mass ratio of 17:1 was reacted with 600-mesh corn stalk powder at 50℃ for 1.3h, then filtered and dried. The dried powder was hydrolyzed with a 35% NaOH solution at a mass ratio of 1:23 at 185℃ for 6.5h. After centrifugation and washing, the powder was dispersed in ethanol, then homogenized under high pressure (1500 bar) and freeze-dried to obtain nano-lignin.

[0122] 2) Nano-lignin, K2CO3 and tert-butyldimethylsilane in a mass ratio of 12:0.22:0.4 were dissolved in DMSO and reacted at 140℃ for 6 h to obtain silane-modified lignin;

[0123] 3) The silane-modified lignin is dispersed in ethanol, and then subjected to ultrasonic treatment (250W, 10min) and freeze-drying to obtain silane-modified nano-lignin.

[0124] The preparation method of the heat-resistant polyurethane sports protective material includes the following steps:

[0125] (1) Preparation of component A: INOVOL C3050A, INOVOL C307, CHE-5107VE, CHP-H45D, ethylene glycol, diethanolamine, triethanolamine, UA-8823LV, and DXCAT were prepared. ® A33, water and silane-modified nano-lignin were added to the reactor, heated to 50°C, stirred at 40 r / min for 50 min to obtain component A;

[0126] (2) Preparation of component B: INOVOL C230, pure MDI and liquefied MDI were stirred at 85℃ for 90 min at a speed of 35 r / min to obtain component B, which had an -NCO content of 21.07%;

[0127] (3) Mix component A and component B at a mass ratio of 100:65, inject into the mold, open the mold and cure after 5 minutes to obtain a heat-resistant polyurethane sports protective material.

[0128] Example 4

[0129] The aforementioned heat-resistant polyurethane sports protective material is made of component A and component B in a mass ratio of 100:60, wherein component A comprises the following raw materials in parts by mass:

[0130] INOVOL C3050A: 25 servings;

[0131] INOVOL C307: 25 servings;

[0132] CHE-5107VE: 35 servings;

[0133] CHP-H45D: 15 servings;

[0134] Ethylene glycol: 3 parts;

[0135] 1,4-Butanediol: 2 parts;

[0136] Triethanolamine: 1 part;

[0137] UA-8823LV: 0.6 units;

[0138] DXCAT ® A33: 1.6 copies;

[0139] Water: 0.6 parts;

[0140] Silane-modified nano-lignin: 18 parts;

[0141] Component B comprises the following parts by weight of raw materials:

[0142] INOVOL C240A: 28 copies;

[0143] Pure MDI: 22 parts;

[0144] Liquefied MDI: 50 parts.

[0145] The method for preparing silane-modified nano-lignin includes the following steps:

[0146] 1) A 40% NaOH solution with a mass ratio of 18:1 was reacted with 400-mesh corn stalk powder at 45℃ for 1.4h, then filtered and dried. The dried powder was then hydrolyzed with a 25% NaOH solution at a mass ratio of 1:24 at 175℃ for 5.5h. After centrifugation and washing, the powder was dispersed in ethanol, then homogenized under high pressure (1000 bar) and freeze-dried to obtain nano-lignin.

[0147] 2) Nano-lignin, K2CO3 and tert-butyldimethylsilane in a mass ratio of 12:0.25:0.45 were dissolved in DMSO and reacted at 135℃ for 5 h to obtain silane-modified lignin;

[0148] 3) The silane-modified lignin is dispersed in ethanol, and then subjected to ultrasonic treatment (250W, 10min) and freeze-drying to obtain silane-modified nano-lignin.

[0149] The preparation method of the heat-resistant polyurethane sports protective material includes the following steps:

[0150] (1) Preparation of component A: INOVOL C3050A, INOVOL C307, CHE-5107VE, CHP-H45D, ethylene glycol, 1,4-butanediol, triethanolamine, UA-8823LV, and DXCAT were prepared. ® A33, water and silane-modified nano-lignin were added to the reactor, heated to 45°C, stirred at 35 r / min for 40 min to obtain component A;

[0151] (2) Preparation of component B: INOVOL C240A, pure MDI and liquefied MDI were stirred at 80℃ for 80 min at a speed of 30 r / min to obtain component B, which had an -NCO content of 21.54%;

[0152] (3) Mix component A and component B at a mass ratio of 100:60, inject into the mold, open the mold and cure after 4 minutes to obtain a heat-resistant polyurethane sports protective material.

[0153] Example 5

[0154] The aforementioned heat-resistant polyurethane sports protective material is made of component A and component B in a mass ratio of 100:58, wherein component A comprises the following raw materials in parts by mass:

[0155] INOVOL C3050A: 20 copies;

[0156] INOVOL C307: 40 copies;

[0157] CHE-5107VE: 20 servings;

[0158] CHP-H45D: 20 servings;

[0159] Ethylene glycol: 2 parts;

[0160] 1,4-Butanediol: 2 parts;

[0161] Diethanolamine: 0.4 parts;

[0162] Triethanolamine: 0.3 parts;

[0163] UA-8823LV: 0.5 copies;

[0164] DXCAT ® A33: 1.8 copies;

[0165] Water: 0.45 parts;

[0166] Silane-modified nano-lignin: 20 parts;

[0167] Component B comprises the following parts by weight of raw materials:

[0168] INOVOL C220: 22 servings;

[0169] Pure MDI: 20 parts;

[0170] Liquefied MDI: 58 parts.

[0171] The method for preparing silane-modified nano-lignin includes the following steps:

[0172] 1) A 50% NaOH solution with a mass ratio of 20:1 was reacted with 500-mesh corn stalk powder at 50℃ for 1.5h, then filtered and dried. The dried powder was then hydrolyzed with a 30% NaOH solution at a mass ratio of 1:25 at 180℃ for 6.5h. After centrifugation and washing, the powder was dispersed in ethanol, then homogenized under high pressure (1000 bar) and freeze-dried to obtain nano-lignin.

[0173] 2) Nano-lignin, K2CO3 and tert-butyldimethylsilane in a mass ratio of 15:0.2:0.5 were dissolved in DMSO and reacted at 140℃ for 6 h to obtain silane-modified lignin;

[0174] 3) The silane-modified lignin is dispersed in ethanol, and then subjected to ultrasonic treatment (250W, 10min) and freeze-drying to obtain silane-modified nano-lignin.

[0175] The preparation method of the heat-resistant polyurethane sports protective material includes the following steps:

[0176] (1) Preparation of component A: INOVOL C3050A, INOVOL C307, CHE-5107VE, CHP-H45D, ethylene glycol, 1,4-butanediol, diethanolamine, triethanolamine, UA-8823LV, and DXCAT were prepared. ® A33, water and silane-modified nano-lignin were added to the reactor, heated to 50°C, stirred at 40 r / min for 50 min to obtain component A;

[0177] (2) Preparation of component B: INOVOL C220, pure MDI and liquefied MDI were stirred at 85℃ for 90 min at a speed of 35 r / min to obtain component B, which had an -NCO content of 22.83%;

[0178] (3) Mix component A and component B at a mass ratio of 100:58, inject into a mold, open the mold and cure after 5 minutes to obtain a heat-resistant polyurethane sports protective material.

[0179] Comparative Example 1

[0180] The difference from Example 4 is that CHE-5107VE in component A is replaced with the same mass of INOVOL C307, otherwise it is the same as Example 4.

[0181] Comparative Example 2

[0182] The difference from Example 4 is that silane-modified nano-lignin is not added to component A, otherwise it is the same as Example 4.

[0183] Comparative Example 3

[0184] The difference from Example 4 is that INOVOL C3050A in component A is replaced with the same mass of INOVOLF330N (purchased from Shandong Yinuowei New Materials Co., Ltd.), otherwise it is the same as Example 4.

[0185] Comparative Example 4

[0186] The difference from Example 4 is that component B is replaced with modified MDI: DG1518 produced by Shandong Yinuowei Polyurethane Co., Ltd., otherwise it is the same as Example 4.

[0187] Comparative Example 5

[0188] The difference from Example 4 is that the silane-modified nano-lignin in component A is replaced with the same mass of unmodified nano-lignin (i.e., the nano-lignin obtained in step 1), otherwise it is the same as Example 4.

[0189] The polyurethane composites prepared in Examples 1-5 and Comparative Examples 1-5 were subjected to performance tests. The performance test results of the examples are shown in Table 1, and the performance test results of the comparative examples are shown in Table 2.

[0190] The testing method is as follows:

[0191] Density: Tested according to GB / T 6343-2009;

[0192] Surface hardness: Tested according to GB / T 531-1999;

[0193] Tensile strength: Tested in accordance with GB / T 6344-2008;

[0194] Elongation at break: Tested according to GB / T 6344-2008;

[0195] Water absorption rate: Tested according to GB / T 8810-2005;

[0196] Impact performance: Tested in accordance with EN1621-3:2018.

[0197] Table 1 Performance test results of the embodiment

[0198]

[0199] As shown in Table 1, the polyurethane composites prepared in Examples 1-5 have excellent physical properties, resistance to damp heat and hydrophobicity, as well as good low-temperature performance and impact resistance. Among them, the hardness changes by no more than 15 Shore C at low and high temperatures compared to room temperature, the impact resistance can reach CE-2 level, and it passes the high and low temperature impact test (EN1621-3:2018).

[0200] Table 2 Comparative Performance Test Results

[0201]

[0202] As can be seen from the comparison between Example 4 and Comparative Example 1, the addition of polyether CHE-5107VE to component A of the present invention can significantly reduce the hardness change of the polyurethane composite material caused by temperature changes, thereby maintaining good protective performance at different temperatures.

[0203] As can be seen from the comparison between Example 4, Comparative Example 2, and Comparative Example 5, the silane-modified nano-lignin added to component A of the present invention can not only improve the hydrophobicity of the product, but also enhance its resistance to damp heat aging.

[0204] As can be seen from the comparison between Example 4 and Comparative Example 3, the CASE polyether added to component A of the present invention can significantly improve the hydrophobicity of the polyurethane composite material while ensuring excellent physical properties.

[0205] As can be seen from the comparison between Example 4 and Comparative Example 4, the B component synthesized in this invention can not only improve the physical properties of the product, but also enhance its impact resistance.

[0206] As can be seen from the comparison between Example 4 and Comparative Example 5, the modification of nano-lignin with silane significantly improves the hydrophobic properties and resistance to humid heat aging of the product.

[0207] In summary, the polyurethane composite material prepared by this invention exhibits excellent physical properties, resistance to damp heat, and hydrophobicity. Sports protective gear materials made from this composite material offer advantages such as lightweight construction, high energy absorption, and the ability to withstand complex and changing environmental conditions.

Claims

1. A temperature resistant polyurethane sports protective material, characterized in that, It is made from component A and component B in a mass ratio of 100:(50-65), wherein component A comprises the following raw materials in parts by mass: Polyether polyol 1: 20-30 parts; Polyether polyol 2: 20-40 parts; Polyether polyol 3: 20-40 parts; Polymer polyol: 10-20 parts; Chain extender: 3-5 parts; Crosslinking agent: 0.5-1 part; Foaming agent: 0.3-0.6 parts; Foam stabilizer: 0.4-0.8 parts; Catalyst: 1-1.8 parts; Modified silane: 10-20 parts; Component B comprises the following parts by weight of raw materials: Polyether polyol 4: 20-30 parts; Pure MDI: 20-30 parts; Liquefied MDI: 40-60 parts; The polyether polyol 1 has a number average molecular weight of 2900-3100, a functionality of 3, and a hydroxyl value of 54.5-57.5 mgKOH / g; The polyether polyol 2 has a number-average molecular weight of 660-750, a functionality of 3, and a hydroxyl value of 225-255 mgKOH / g; The polyether polyol 3 has a number average molecular weight of 1530-1600, a functionality of 3, and a hydroxyl value of 105.0-110.0 mgKOH / g; The polyether polyol 4 has a number average molecular weight of 1000-4000, a functionality of 2, and a hydroxyl value of 28-112 mgKOH / g; The modified silane is silane-modified nano-lignin, and the preparation method of the silane-modified nano-lignin includes the following steps: 1) A 30-50% NaOH solution with a mass ratio of (15-20):1 is reacted with 400-600 mesh corn stalk powder at 45-50℃ for 1-1.5h, followed by filtration and drying. The dried powder is then hydrolyzed with a 25-35% NaOH solution at a mass ratio of 1:(20-25) at 175-185℃ for 5.5-6.5h. After centrifugation and washing, the powder is dispersed in ethanol, then homogenized and freeze-dried to obtain nano-lignin. 2) Nano-lignin, K2CO3 and tert-butyldimethylsilane in a mass ratio of (10-15):(0.2-0.25):(0.4-0.5) are dissolved in DMSO and reacted at 130-140℃ for 4-6 h to obtain silane-modified lignin; 3) The silane-modified lignin is dispersed in ethanol, and then subjected to ultrasonic treatment and freeze drying to obtain silane-modified nano-lignin.

2. The temperature resistant polyurethane sports protective material according to claim 1, characterized in that, The polymer polyol has a functionality of 3, a hydroxyl value of 19.0-23.0 mgKOH / g, and a solid content of 41.0-45.0%.

3. The temperature-resistant polyurethane sports protective material according to claim 1, characterized in that, The chain extender is one or both of ethylene glycol and 1,4-butanediol.

4. The heat-resistant polyurethane sports protective material according to claim 1, characterized in that, The crosslinking agent is one or both of diethanolamine or triethanolamine.

5. The heat-resistant polyurethane sports protective material according to claim 1, characterized in that, The foaming agent is water.

6. The heat-resistant polyurethane sports protective material according to claim 1, characterized in that, The foam stabilizer mentioned is an organosilicon foam stabilizer.

7. The heat-resistant polyurethane sports protective material according to claim 1, characterized in that, The catalyst is A33.

8. A method for preparing a heat-resistant polyurethane sports protective material according to any one of claims 1-7, characterized in that, Includes the following steps: (1) Preparation of component A: Polyether polyol 1, polyether polyol 2, polyether polyol 3, polymer polyol, chain extender, crosslinking agent, foaming agent, foam stabilizer, catalyst and modified silane are added into the reactor, heated to 40-50℃, stirred at 35-40r / min for 40-50min to obtain component A; (2) Preparation of component B: Polyether polyol 4, pure MDI and liquefied MDI are stirred at 80-85℃ and 30-35r / min for 80-90min to obtain component B; (3) Mix components A and B evenly according to the mass ratio, inject into the mold, open the mold and cure after 4-5 minutes to obtain heat-resistant polyurethane sports protective material.

9. The application of the heat-resistant polyurethane sports protective material according to any one of claims 1-7, characterized in that, Materials used in sports protective gear.

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