High-Slip-Resistant and Durable Polyurethane Microporous Shoe Soles: Resins, Preparation Methods, and Applications

Abstract

This invention belongs to the field of polyurethane resin technology, specifically relating to a high-slip-resistant and durable polyurethane microporous sole resin for shoe soles, its preparation method, and its application. The high-slip-resistant and durable polyurethane microporous sole resin is composed of component A and component B. Component A includes the following raw materials: polyester polyol a, polyester polyol b, polyether polyol, chain extender, foam leveler, catalyst, foaming agent, polyether-modified siloxane, and benzyl-containing ester plasticizer. Component B includes the following raw materials: polyester polyol a, polyester polyol b, polyether polyol, benzyl-containing ester plasticizer, and isocyanate. The high-slip-resistant and durable polyurethane microporous sole resin of this invention introduces a benzyl-containing plasticizer and polyether-modified siloxane into the polyurethane system, resulting in a sole product with excellent slip resistance and durability, good dimensional stability, excellent mechanical properties, and a dense cell structure. This invention also provides a method for preparing the resin and its application.

Description

Technical Field

[0001] This invention belongs to the field of polyurethane resin technology, specifically relating to a high anti-slip and durable polyurethane microporous shoe sole resin, its preparation method, and its application. Background Technology

[0002] With the rise of the global sports industry, outdoor activities, and healthy lifestyles, consumers are increasingly demanding higher functionality from sports shoes, safety shoes, casual shoes, and work shoes. Among these, the anti-slip performance and durability of the soles have become core indicators for measuring footwear product standards. Especially on wet and slippery surfaces and complex terrain, excellent anti-slip performance can effectively prevent slipping accidents and ensure personal safety, while durability directly determines the lifespan of the soles.

[0003] Currently available shoe sole anti-slip designs, especially sole patterns and materials, have the following limitations:

[0004] Homogeneous Tread Pattern Designs and Mismatched Working Conditions: Most shoe sole patterns follow traditional, universal designs, such as simple herringbone or wave patterns. The depth, width, angle, and distribution of these grooves have not been optimized for different working environments (such as oily and watery kitchens, slaughterhouses, machining workshops, and slippery outdoor surfaces). In complex fluid media, universal patterns lack sufficient drainage and oil-removal capabilities, easily forming "water films" or "oil films," leading to hydraulic slippage and a significant decrease in anti-slip performance.

[0005] The contradiction between slip resistance and durability in shoe sole materials: High slip resistance typically requires sole materials with high viscosity, low hardness, and a high coefficient of friction, such as some soft rubber compounds. However, these materials often have poor abrasion resistance, tear resistance, and support, failing to meet the high requirements for durability and foot protection in shoe soles. Conversely, materials with good abrasion resistance (such as certain PU, TPU, or hard rubber) often have high hardness, low coefficient of friction, and poor slip resistance. This contradiction in material performance is the core challenge currently facing shoe soles.

[0006] CN116622050A discloses a low-density wear-resistant and anti-slip polyurethane shoe sole resin and its preparation method. A diol containing phenyl groups is introduced into the molecular structure to synthesize polyol P1, which is used in components A and B respectively. Polyol P2, containing rigid benzene ring groups, is introduced into component A. Combined with high-performance wear-resistant agent N4-9000, silicone oil with excellent opening and foaming effects, and polyether polyol, the effective dosage of each raw material synergistically enhances the product's wear resistance and anti-slip properties. The raw materials are safe and environmentally friendly, and the production process is simple, efficient, energy-saving, and reduces consumption. However, both the polyester polyols P1 and P2 used contain benzene ring structures, resulting in high material viscosity. This makes the preparation process difficult and costly. Furthermore, the rigid benzene ring structure leads to poor flexibility in the resulting product, low reactivity during molding, and stringent requirements for temperature and catalyst.

[0007] CN111205626A discloses a non-slip polyurethane microporous shoe sole resin and its preparation method. The method involves melting rubber and polyurethane, then introducing polydimethylsiloxane as component A. Ethylene-vinyl acetate copolymer, Phylon material, TPR material, polydimethylsiloxane, and modified nano-silica are used as component B. After mixing components A and B, octyl epoxy stearate, modifying additives, carboxymethyl cellulose, bamboo charcoal fiber, and bamboo pulp fiber are introduced and mixed in stages at controlled temperatures. Finally, foaming and polishing are performed to obtain the shoe sole product. Through the proportions of the raw materials, the resulting shoe sole combines the advantages of five materials: polyurethane, TPR material, ethylene-vinyl acetate copolymer, Phylon material, and rubber, thus possessing properties such as softness, wear resistance, low water absorption, and slip resistance. Simultaneously, the wear resistance of the shoe sole is improved through modified silica and modifying additives. However, the preparation process is complex, requires many types of raw materials, has a long preparation cycle, high equipment requirements, high cost, and is not easily mass-produced.

[0008] Therefore, there is an urgent need to develop a shoe sole that combines high slip resistance and durability, breaking through the traditional constraints of material performance and structural design, providing slip resistance in various dangerous and slippery environments, and being durable and long-lasting. Summary of the Invention

[0009] To overcome the aforementioned deficiencies in the prior art, this invention provides a high-slip-resistant and durable polyurethane microporous sole resin. A benzyl-containing plasticizer and a polyether-modified siloxane are introduced and combined with the polyurethane system. The resulting sole product exhibits excellent slip resistance and durability, as well as good dimensional stability, superior mechanical properties, and a dense cell structure. This invention also provides a method for preparing the resin and its applications.

[0010] The high anti-slip and durable polyurethane microporous shoe sole resin of the present invention is composed of component A and component B in a mass ratio of 100:(60-90). Component A includes the following raw materials in parts by mass:

[0011] Polyester polyol a: 70-90 parts;

[0012] Polyester polyol b: 5-20 parts;

[0013] Polyether polyol: 5-10 parts;

[0014] Chain extender: 5-10 parts;

[0015] Foaming agent: 0.3-0.6 parts;

[0016] Catalyst: 0.6-1.5 parts;

[0017] Foaming agent: 0.2-0.5 parts;

[0018] Polyether-modified siloxane: 0.3-0.8 parts;

[0019] Ester-type plasticizers containing benzyl groups: 5-10 parts;

[0020] In component A, the sum of the mass fractions of polyester polyol a, polyester polyol b, and polyether polyol is 100 parts.

[0021] Component B comprises the following raw materials in parts by weight:

[0022] Polyester polyol a: 10-20 parts;

[0023] Polyester polyol b: 5-10 parts;

[0024] Polyether polyol: 5-10 parts;

[0025] Ester-type plasticizers containing benzyl groups: 5-10 parts;

[0026] Isocyanate: 55-70 parts;

[0027] The polyester polyol a is prepared by polycondensation reaction of difunctional small molecule polyol a and adipic acid, with a functionality of 2 and a number-average molecular weight of 3000-4000 g / mol. The small molecule polyol a is one of ethylene glycol, diethylene glycol, and 1,4-butanediol, preferably one or more of PE-25303, PE-2040, PE-2540, and PE-2440 produced by Shandong Yinuowei Polyurethane Co., Ltd.

[0028] The polyester polyol b is prepared by polycondensation reaction of a mixture of difunctional small molecule polyol b and trifunctional small molecule polyol c with adipic acid. The functionality is >2, the number average molecular weight is 1200-2000 g / mol, the small molecule polyol b is one of ethylene glycol and diethylene glycol, and the small molecule polyol c is one of glycerol and trimethylolpropane. Preferably, it is one or more of PE-2520-03, PE-2512-04 and PE-2325 produced by Shandong Yinuowei Polyurethane Co., Ltd.

[0029] The polyether polyol has a functionality of 2-3, a number average molecular weight of 4000-6000 g / mol, and a primary hydroxyl molar content of >70%. Preferably, it is one or more of EP-3600, EP-330NG, ED-28 produced by Shandong Lanxing Dongda Chemical Co., Ltd., and KE-510 produced by Keliya Polyol (Nanjing) Co., Ltd.

[0030] The polyether-modified siloxane is prepared by an addition reaction of a hydrogen-containing siloxane and an EO / PO copolyallyl-terminated polyether. The number-average molecular weight of the polyether-modified siloxane is 1700-2700 g / mol. The specific preparation method of the polyether-modified siloxane is as follows: Hydrogen-containing siloxane and an EO / PO copolyallyl-terminated polyether are added to a reactor at a molar ratio of 1.0:(1.0-2.0), along with 30 ppm of an inhibitor alkynol and 15 ppm of a platinum catalyst, accounting for 30 ppm of the total weight of the reactants. The mixture is heated to 100-110℃ and reacted for 3-5 hours to obtain polyether-modified siloxanes. Among them, the preferred hydrogen-containing siloxane is 1,1,3,3,5,5-hexamethyltrisiloxane, CAS: 1189-93-1, with a molecular weight of 208.48 g / mol. The number average molecular weight of the EO and PO copolyallyl-terminated polyether is 1400-1500 g / mol, preferably allyl alcohol polyether F-6 from Sanda Chemical Nantong Co., Ltd., with a number average molecular weight of 1500 g / mol.

[0031] The chain extender is one or two of ethylene glycol, diethylene glycol, and 1,4-butanediol.

[0032] The foam stabilizer is a polysiloxane-olefin oxide block copolymer, preferably DC2525 and DC193 from Air Products, Inc.

[0033] The catalyst is one of the tertiary amine catalysts DXD-07C and DXD-01C, preferably DXD-01C produced by Shandong Yinuowei Polyurethane Co., Ltd.; the foaming agent is water.

[0034] The benzyl-containing ester plasticizer is butylbenzylcyclohexane-1,2-dicarboxylic acid ester with a number-average molecular weight of 318 g / mol, preferably Santicizer® Platinum P-1400, purchased from Nanjing Gutian Chemical Co., Ltd., and its molecular structure is shown below:

[0035] .

[0036] The isocyanate is a mixture of 4,4-diphenylmethane diisocyanate and carbodiimide-modified isocyanate, and the 4,4-diphenylmethane diisocyanate and carbodiimide-modified isocyanate can be mixed in any proportion.

[0037] The preparation method of the high anti-slip and durable polyurethane microporous shoe sole resin includes the following steps:

[0038] (1) Preparation of component A: Polyester polyol a, polyester polyol b, polyether polyol, chain extender, foam leveler, catalyst, foaming agent, polyether modified siloxane, and ester plasticizer containing benzyl structure are added into the reactor and stirred at 40-60℃ for 1-2 hours to obtain component A.

[0039] (2) Preparation of component B: Polyester polyol a, polyester polyol b, polyether polyol and ester plasticizer containing benzyl structure are put into the reactor, the material temperature is controlled at 40-50℃, isocyanate is added, and after reacting at 70-80℃ for 2-3h, component B with -NCO content of 16.9-22.6wt.% is obtained.

[0040] The application of the high anti-slip and durable polyurethane microporous shoe sole resin is for the preparation of polyurethane microporous shoe soles. The preparation method is as follows: Component A and Component B are injected into the material tank of a low-pressure casting machine respectively. Component A and Component B are mixed at a mass ratio of 100:(60-90) and then injected into a mold at 45-60℃. The mold is opened after 2-4 minutes to obtain the high anti-slip and durable polyurethane microporous shoe sole.

[0041] Compared with the prior art, the beneficial effects of the present invention are as follows:

[0042] (1) In this invention, polyether-modified siloxane is introduced into component A. By optimizing the amount and structure of polyether-modified siloxane, the hydrophobicity of the product is improved. The siloxane segments in the polyether-modified siloxane structure can provide good hydrophobicity and low surface energy for the sole. The grafted EO and PO copolymerized polyether segments, by utilizing the different molar ratios of EO and PO in the modified siloxane, not only achieve good miscibility between the siloxane segments and the matrix polyester polyol, but also utilize the branched methyl groups in the grafted PO segments to make the sole have excellent hydrophobicity and low surface energy, thereby significantly improving the anti-slip performance of the sole on wet surfaces.

[0043] (2) The present invention introduces ester plasticizers containing benzyl structures into components A and B simultaneously. The unique molecular structure and steric hindrance effect of the plasticizer reduce the hydrolysis rate of ester bonds, delay the penetration of water molecules, and improve the durability in wet and slippery environments. The benzyl structure in the plasticizer gives the sole good flexibility. The combination of the benzyl structure and the cyclohexane structure improves the low-temperature flexibility of the sole, making the sole less prone to cracking in cold environments and improving the durability of the sole in cold environments.

[0044] (3) The present invention utilizes the synergistic effect of polyether-modified siloxane and ester-type plasticizer containing benzyl structure to endow the product with good anti-slip performance and durability. When applied to the preparation of polyurethane microporous shoe sole, the resulting product has good dimensional stability, excellent mechanical properties and dense cell structure, which can meet the requirements of medium and high-end, high-quality shoe models.

[0045] (4) The preparation method of the high anti-slip and durable polyurethane microporous shoe sole resin of the present invention is simple. Detailed Implementation

[0046] The present invention will be further described below with reference to the embodiments and comparative examples. Unless otherwise specified, the raw materials used in the embodiments and comparative examples are all conventional commercial raw materials, and the process methods used are all conventional methods in the art unless otherwise specified. The parts involved in the raw materials in the embodiments and comparative examples are all parts by mass.

[0047] The raw materials used in the examples and comparative examples are described below:

[0048] PE-25303: Polyester polyol a, functionality 2, number average molecular weight 3000 g / mol, Shandong Yinuowei Polyurethane Co., Ltd.

[0049] PE-2040: Polyester polyol a, functionality 2, number average molecular weight 4000 g / mol, Shandong Yinuowei Polyurethane Co., Ltd.

[0050] PE-2540: Polyester polyol a, functionality 2, number average molecular weight 4000 g / mol, Shandong Yinuowei Polyurethane Co., Ltd.

[0051] PE-2440: Polyester polyol a, functionality 2, number average molecular weight 4000 g / mol, Shandong Yinuowei Polyurethane Co., Ltd.

[0052] PE-2520-03: Polyester polyol b, functionality 2.03, number average molecular weight 2000 g / mol, Shandong Yinuowei Polyurethane Co., Ltd.

[0053] PE-2512-04: Polyester polyol b, functionality 2.04, number average molecular weight 1200 g / mol, Shandong Yinuowei Polyurethane Co., Ltd.

[0054] PE-2325: Polyester polyol b, functionality 2.06, number average molecular weight 2000 g / mol, Shandong Yinuowei Polyurethane Co., Ltd.

[0055] EP-3600, polyether polyol, functionality 3, number average molecular weight 6000 g / mol, Shandong Lanxing Dongda Chemical Co., Ltd.;

[0056] EP-330NG, polyether polyol, functionality 3, number average molecular weight 5000 g / mol, Shandong Lanxing Dongda Chemical Co., Ltd.;

[0057] ED-28, polyether polyol, functionality 2, number average molecular weight 4000 g / mol, Shandong Lanxing Dongda Chemical Co., Ltd.;

[0058] KE-510, polyether polyol, functionality 2, number average molecular weight 4000 g / mol, KELIA Polyol (Nanjing) Co., Ltd.;

[0059] DC2525: Foaming agent, Air Products, Inc., USA;

[0060] DC193: Foaming agent, Air Products, Inc., USA;

[0061] DXD-01C: Catalyst, Shandong Yinuowei Polyurethane Co., Ltd.;

[0062] MDI-100: 4,4-Diphenylmethane diisocyanate, Wanhua Chemical Group Co., Ltd.;

[0063] CDMDI-100L: Carbodiimide-modified isocyanate, Wanhua Chemical Group Co., Ltd.;

[0064] EO and PO copolyallyl-terminated polyether: allyl alcohol polyether F-6, number average molecular weight 1500 g / mol, molecular formula CH2=CH-CH2O(C3H6O). m (C2H4O) n H, Sanda Chemical Nantong Co., Ltd.;

[0065] Butylbenzylcyclohexane-1,2-dicarboxylic acid ester: an ester-type plasticizer containing a benzyl group (Santicizer) ® PlatinumP-1400, with a number-average molecular weight of 318 g / mol, was purchased from Nanjing Gutian Chemical Co., Ltd.

[0066] The preparation process of the polyether-modified siloxane used in the examples and comparative examples is shown below.

[0067] Polyether-modified siloxane a, with a number-average molecular weight of 1700 g / mol:

[0068] 85.1 kg of allyl alcohol polyether F-6 was added to the reactor, followed by 11.8 kg of 1,1,3,3,5,5-hexamethyltrisiloxane. An inhibitor alkynyl alcohol of 30 ppm of the total weight of the reactants and a platinum catalyst of 15 ppm of the total weight of the reactants were added. The temperature was raised to 100°C and the reaction was carried out for 3 hours. The number average molecular weight of the product obtained by GPC determination was 1700 g / mol, which met the requirements.

[0069] Polyether-modified siloxane b, number average molecular weight 2400 g / mol:

[0070] 89.5 kg of allyl alcohol polyether F-6 was added to the reactor, followed by 8.27 kg of 1,1,3,3,5,5-hexamethyltrisiloxane. An inhibitor alkynyl alcohol of 30 ppm of the total weight of the reactants and a platinum catalyst of 15 ppm of the total weight of the reactants were added. The temperature was raised to 105°C and the reaction was carried out for 4 hours. The number average molecular weight of the product obtained by GPC determination was 2400 g / mol, which met the requirements.

[0071] Polyether-modified siloxane C, number average molecular weight 2700 g / mol:

[0072] 91.95 kg of allyl alcohol polyether F-6 was added to the reactor, followed by 6.38 kg of 1,1,3,3,5,5-hexamethyltrisiloxane. An inhibitor alkynyl alcohol of 30 ppm of the total weight of the reactants and a platinum catalyst of 15 ppm of the total weight of the reactants were added. The temperature was raised to 110°C and the reaction was carried out for 5 h. The number average molecular weight of the product obtained by GPC determination was 2700 g / mol.

[0073] Example 1

[0074] The preparation method of the high anti-slip and durable polyurethane microporous shoe sole resin includes the following steps:

[0075] (1) Preparation of component A: According to the mass parts, start stirring and add 70 parts of PE-25303, 20 parts of PE-2512-04, 10 parts of KE-510, 10 parts of 1,4-butanediol, 0.3 parts of polyether modified siloxane a, 0.3 parts of DC193, 5 parts of butylbenzylcyclohexane-1,2-dicarboxylic acid ester, 0.6 parts of DXD-01C and 0.2 parts of water into the reactor in sequence. After stirring at 40°C for 1 hour, component A is obtained.

[0076] (2) Preparation of component B: According to the mass parts, 16 parts of PE-2440, 7 parts of PE-2325, 7 parts of KE-510 and 8 parts of butylbenzylcyclohexane-1,2-dicarboxylic acid ester were added into the reactor in sequence, the stirring was turned on, and then the material temperature was raised to 40°C. 55 parts of MDI-100 and 7 parts of CDMDI-100L were added. After reacting at 75°C for 2.5h, component B with a -NCO content of 19.8wt.% was obtained.

[0077] The application of the aforementioned high-slip-resistant and durable polyurethane microporous shoe sole resin includes the following steps:

[0078] Components A and B are injected into the material tank of a low-pressure casting machine. Components A and B are quickly mixed at a mass ratio of 100:60 and then injected into a mold at 45°C. The mold is opened after 3 minutes to obtain a high-slip and durable polyurethane microporous shoe sole.

[0079] Example 2

[0080] The preparation method of the high anti-slip and durable polyurethane microporous shoe sole resin includes the following steps:

[0081] (1) Preparation of component A: According to the mass parts, 85 parts of PE-2440, 10 parts of PE-2520-03, 5 parts of KE-510, 7.5 parts of ethylene glycol, 0.6 parts of polyether modified siloxane a, 0.6 parts of DC2525, 10 parts of butylbenzylcyclohexane-1,2-dicarboxylic acid ester, 1.3 parts of DXD-07C and 0.2 parts of water were added into the reactor in sequence. After stirring at 60°C for 2 hours, component A was obtained.

[0082] (2) Preparation of component B: According to the mass parts, 16 parts of PE-2440, 7 parts of PE-2325, 7 parts of KE-510 and 8 parts of butylbenzylcyclohexane-1,2-dicarboxylic acid ester were added into the reactor in sequence, the stirring was turned on, and then the temperature was lowered to 50°C. 55 parts of MDI-100 and 7 parts of CDMDI-100L were added. After reacting at 75°C for 2.5h, component B with a -NCO content of 19.8wt.% was obtained.

[0083] The application of the aforementioned high-slip-resistant and durable polyurethane microporous shoe sole resin includes the following steps:

[0084] Components A and B are injected into the material tank of a low-pressure casting machine. Components A and B are quickly mixed at a mass ratio of 100:60 and then injected into a mold at 50°C. The mold is opened after 4 minutes to obtain a high-slip and durable polyurethane microporous shoe sole.

[0085] Example 3

[0086] The preparation method of the high anti-slip and durable polyurethane microporous shoe sole resin includes the following steps:

[0087] (1) Preparation of component A: According to the mass parts, 85 parts of PE-25303, 10 parts of PE-2520-03, 5 parts of ED-28, 8 parts of ethylene glycol, 0.4 parts of polyether modified siloxane b, 0.4 parts of DC2525, 10 parts of butylbenzylcyclohexane-1,2-dicarboxylic acid ester, 1.2 parts of DXD-01C and 0.3 parts of water were added into the reactor in sequence. After stirring at 60°C for 2 hours, component A was obtained.

[0088] (2) Preparation of component B: According to the mass parts, 20 parts of PE-2440, 10 parts of PE-2512-04, 10 parts of EP-3600 and 5 parts of butylbenzylcyclohexane-1,2-dicarboxylic acid ester were added into the reaction vessel in sequence, the stirring was turned on, and then the temperature was lowered to 40°C. 50 parts of MDI-100 and 5 parts of CDMDI-100L were added. After reacting at 80°C for 3 hours, component B with a -NCO content of 16.9 wt.% was obtained.

[0089] The application of the aforementioned high-slip-resistant and durable polyurethane microporous shoe sole resin includes the following steps:

[0090] Components A and B are injected into the material tank of a low-pressure casting machine. Components A and B are quickly mixed at a mass ratio of 100:80 and then injected into a mold at 50°C. The mold is opened after 4 minutes to obtain a high-slip and durable polyurethane microporous shoe sole.

[0091] Example 4

[0092] The preparation method of the high anti-slip and durable polyurethane microporous shoe sole resin includes the following steps:

[0093] (1) Preparation of component A: According to the mass parts, 80 parts of PE-2540, 12 parts of PE-2512-04, 8 parts of EP-330NG, 3 parts of ethylene glycol, 2 parts of 1,4-butanediol, 0.8 parts of polyether modified siloxane b, 0.6 parts of DC2525, 7 parts of butylbenzylcyclohexane-1,2-dicarboxylic acid ester, 1.2 parts of DXD-07C and 0.4 parts of water were added to the reactor in sequence and stirred at 60°C for 1.5 h to obtain component A;

[0094] (2) Preparation of component B: According to the mass parts, 20 parts of PE-2440, 10 parts of PE-2512-04, 10 parts of EP-3600 and 5 parts of butylbenzylcyclohexane-1,2-dicarboxylic acid ester were added into the reactor in sequence, the stirring was turned on, and then the temperature was lowered to 45°C. 50 parts of MDI-100 and 5 parts of CDMDI-100L were added. After reacting at 80°C for 3 hours, component B with a -NCO content of 16.9 wt.% was obtained.

[0095] The application of the aforementioned high-slip-resistant and durable polyurethane microporous shoe sole resin includes the following steps:

[0096] Components A and B are injected into the material tank of a low-pressure casting machine. Components A and B are quickly mixed at a mass ratio of 100:64 and then injected into a mold at 60°C. The mold is opened after 2 minutes to obtain a high-slip and durable polyurethane microporous shoe sole.

[0097] Example 5

[0098] The preparation method of the high anti-slip and durable polyurethane microporous shoe sole resin includes the following steps:

[0099] (1) Preparation of component A: According to the mass parts, 80 parts of PE-2440, 12 parts of PE-2512-04, 8 parts of ED-28, 10 parts of diethylene glycol, 0.3 parts of polyether modified siloxane C, 0.6 parts of DC2525, 7 parts of butylbenzylcyclohexane-1,2-dicarboxylic acid ester, 1.1 parts of DXD-01C and 0.4 parts of water were added into the reactor in sequence. After stirring at 60°C for 1 hour, component A was obtained.

[0100] (2) Preparation of component B: According to the mass parts, 20 parts of PE-2440, 10 parts of PE-2512-04, 10 parts of EP-3600 and 5 parts of butylbenzylcyclohexane-1,2-dicarboxylic acid ester were added into the reaction vessel in sequence, the stirring was turned on, and then the temperature was lowered to 40°C. 50 parts of MDI-100 and 5 parts of CDMDI-100L were added. After reacting at 80°C for 3 hours, component B with a -NCO content of 16.9 wt.% was obtained.

[0101] The application of the aforementioned high-slip-resistant and durable polyurethane microporous shoe sole resin includes the following steps:

[0102] Components A and B are injected into the material tank of a low-pressure casting machine. Components A and B are quickly mixed at a mass ratio of 100:90 and then injected into a mold at 60°C. The mold is opened after 2 minutes to obtain a high-slip and durable polyurethane microporous shoe sole.

[0103] Example 6

[0104] The preparation method of the high anti-slip and durable polyurethane microporous shoe sole resin includes the following steps:

[0105] (1) Preparation of component A: According to the mass parts, 90 parts of PE-25303, 5 parts of PE-2512-04, 5 parts of KE-510, 6 parts of ethylene glycol, 0.5 parts of polyether modified siloxane c, 0.6 parts of DC193, 10 parts of butyl benzyl cyclohexane-1,2-dicarboxylic acid ester, 1.5 parts of DXD-07C and 0.5 parts of water were added into the reactor in sequence and stirred at 50°C for 1 h to obtain component A;

[0106] (2) Preparation of component B: According to the mass parts, 10 parts of PE-2040, 5 parts of PE-2325, 5 parts of KE-510 and 10 parts of butylbenzylcyclohexane-1,2-dicarboxylic acid ester were added into the reaction vessel in sequence, the stirring was turned on, and then the temperature was lowered to 40°C. 60 parts of MDI-100 and 10 parts of CDMDI-100L were added. After reacting at 70°C for 2 hours, component B with a -NCO content of 22.6 wt.% was obtained.

[0107] The application of the aforementioned high-slip-resistant and durable polyurethane microporous shoe sole resin includes the following steps:

[0108] Components A and B are injected into the material tank of a low-pressure casting machine. Components A and B are quickly mixed at a mass ratio of 100:75 and then injected into a mold at 50°C. The mold is opened after 4 minutes to obtain a high-slip and durable polyurethane microporous shoe sole.

[0109] Comparative Example 1

[0110] This comparative example is the same as Example 3, except that the polyether-modified siloxane in component A is removed, while the raw materials and steps of the remaining components are the same as in Example 3.

[0111] Comparative Example 2

[0112] This comparative example is the same as Example 3, except that the ester plasticizer containing the benzyl structure in component B is removed and added entirely to component A. The raw materials and steps of the remaining components are the same as in Example 3.

[0113] The preparation method of the high anti-slip and durable polyurethane microporous shoe sole resin includes the following steps:

[0114] (1) Preparation of component A: According to the mass parts, 85 parts of PE-25303, 10 parts of PE-2520-03, 5 parts of ED-28, 9.5 parts of ethylene glycol, 0.4 parts of polyether modified siloxane b, 0.4 parts of DC2525, 15 parts of butylbenzylcyclohexane-1,2-dicarboxylic acid ester, 1.2 parts of DXD-01C and 0.3 parts of water were added into the reactor in sequence. After stirring at 60°C for 2 hours, component A was obtained.

[0115] (2) Preparation of component B: According to the mass parts, 20 parts of PE-2440, 10 parts of PE-2512-04 and 10 parts of EP-3600 were added into the reactor in sequence, the stirring was turned on, and then the temperature was lowered to 40°C. 50 parts of MDI-100 and 5 parts of CDMDI-100L were added. After reacting at 80°C for 3 hours, component B with a -NCO content of 17.8wt.% was obtained.

[0116] The application of the aforementioned high-slip-resistant and durable polyurethane microporous shoe sole resin includes the following steps:

[0117] Components A and B are injected into the material tank of a low-pressure casting machine. Components A and B are quickly mixed at a mass ratio of 100:80 and then injected into a mold at 50°C. The mold is opened after 4 minutes to obtain a high-slip and durable polyurethane microporous shoe sole.

[0118] Comparative Example 3

[0119] The preparation method of the high anti-slip and durable polyurethane microporous shoe sole resin includes the following steps:

[0120] (1) Preparation of component A: According to the mass parts, 85 parts of PE-25303, 10 parts of PE-2520-03, 5 parts of ED-28, 10 parts of butylbenzylcyclohexane-1,2-dicarboxylic acid ester, 8.2 parts of ethylene glycol, 0.4 parts of DC2525, 2 parts of polyether modified siloxane b, 1.2 parts of DXD-01C and 0.3 parts of water were added into the reactor in sequence. After stirring at 60°C for 2 hours, component A was obtained.

[0121] (2) Preparation of component B: According to the mass parts, 24.5 parts of PE-2440, 10 parts of PE-2512-04 and 10 parts of EP-3600 were added into the reactor in sequence, the stirring was turned on, and then the temperature was lowered to 40°C. 50 parts of MDI-100 and 5 parts of CDMDI-100L were added. After reacting at 80°C for 3 hours, component B with a -NCO content of 16.9 wt.% was obtained.

[0122] The application of the aforementioned high-slip-resistant and durable polyurethane microporous shoe sole resin includes the following steps:

[0123] Components A and B are injected into the material tank of a low-pressure casting machine. Components A and B are quickly mixed at a mass ratio of 100:80 and then injected into a mold at 50°C. The mold is opened after 4 minutes to obtain a high-slip and durable polyurethane microporous shoe sole.

[0124] Comparative Example 4

[0125] This comparative example is the same as Example 3, except that the type of polyether-modified siloxane in component A is changed to EO chain-extended polyether-modified siloxane. The raw materials and steps of the remaining components are the same as in Example 3. The preparation process of EO chain-extended polyether-modified siloxane is the same as that of polyether-modified siloxane. The EO chain-extended polyether is APEG-1000 with a number average molecular weight of 1000 g / mol, produced by Nantong Arches Chemical Co., Ltd. The number average molecular weight of the modified siloxane prepared is 2200 g / mol.

[0126] Comparative Example 5

[0127] The preparation method of the high anti-slip and durable polyurethane microporous shoe sole resin includes the following steps:

[0128] (1) Preparation of component A: According to the mass parts, 85 parts of PE-25303, 10 parts of PE-2520-03, 5 parts of ED-28, 8 parts of ethylene glycol, 0.4 parts of polyether modified siloxane b, 0.4 parts of DC2525, 10 parts of dioctyl maleate, 1.2 parts of DXD-01C and 0.3 parts of water were added into the reactor in sequence. After stirring at 60°C for 2 hours, component A was obtained.

[0129] (2) Preparation of component B: According to the mass parts, 20 parts of PE-2440, 10 parts of PE-2512-04, 10 parts of EP-3600 and 5 parts of dioctyl maleate were added into the reaction vessel in sequence, the stirring was turned on, and then the temperature was lowered to 40°C. 50 parts of MDI-100 and 5 parts of CDMDI-100L were added. After reacting at 80°C for 3 hours, component B with a -NCO content of 16.9wt.% was obtained.

[0130] The application of the aforementioned high-slip-resistant and durable polyurethane microporous shoe sole resin includes the following steps:

[0131] Components A and B are injected into the material tank of a low-pressure casting machine. Components A and B are quickly mixed at a mass ratio of 100:80 and then injected into a mold at 50°C. The mold is opened after 4 minutes to obtain a high-slip and durable polyurethane microporous shoe sole.

[0132] The performance of the high-slip-resistant and durable polyurethane microporous soles prepared in Examples 1-6 and Comparative Examples 1-5 was tested. The test results are shown in Tables 1-2. The product density was tested according to GB / T 6343-2009, and the hardness was tested according to GB / T 3903.4-2017. The tensile strength, elongation, right-angle tear strength, and flexural cycles were tested according to GB / T 20991-2007. The flexural cycles test under wet slip conditions (measuring the wet slip durability of the sole) was conducted by first pretreating the product and placing it in a constant temperature and humidity chamber (temperature 60℃, humidity 80%) for 30 days before testing. The flexural cycles test under low temperature (-20℃) conditions (measuring the low temperature durability of the sole) was conducted by testing the prepared high-slip-resistant and durable polyurethane soles at -20℃. The slip resistance test was conducted according to the HG / T3780-2005 test standard "Test Method for Static Anti-slip Performance of Footwear".

[0133] Table 1 Performance Test Table of Products from Examples 1-6

[0134]

[0135] Table 2 Performance Test Table of Comparative Examples 1-5

[0136]

[0137] As shown in Table 1, the products obtained in Examples 1-6 of this invention have a density of 800-835 kg / m³. 3 With a hardness of 68-75C, the tensile strength, tear strength, elongation, and flexural strength all meet the technical specifications of the shoe sole. Polyether-modified siloxane and ester-type plasticizers containing benzyl structures are introduced into the polyurethane system. By utilizing the synergistic effect of the two, the dry / wet friction coefficient of the shoe sole is improved, significantly enhancing the anti-slip performance of the shoe sole on wet and oily surfaces. At the same time, the two work together to improve the durability of the shoe sole under wet and low temperature conditions, as well as the number of flex cycles under wet conditions and the number of flex cycles under low temperature (-20℃) conditions.

[0138] As can be seen from Tables 1 and 2, compared with Comparative Example 1, Example 3 has superior flexural cycles under wet and low temperature conditions and a high dry / wet friction coefficient. This is because the branched methyl groups in the siloxane segments of the polyether-modified siloxane and the PO segments of the polyether give the product good hydrophobicity and low surface energy, thereby giving the sole better anti-slip properties and durability.

[0139] Compared with Comparative Example 2, Example 3 exhibits superior flexibility, wet slip resistance, and flexural cycles under normal temperature and low temperature conditions, as well as a high dry / wet friction coefficient. This is because Example 3 introduces ester-type plasticizers containing benzyl structures into both components A and B. Compared to adding them alone to component A, the ester-type plasticizers containing benzyl structures added to component B not only have good compatibility with component B but also improve the storage stability of component B and reduce the generation of brittle polyurea structures in component B, thereby giving the sole better flexibility, superior slip resistance, and durability.

[0140] Compared with Example 3, the mechanical properties and flexural properties of the product in Comparative Example 3 decreased significantly. The reason is that the amount of polyether-modified siloxane added in Comparative Example 3 was higher. The excessive flexible segments reduced the tensile strength and right-angle tear strength of the product. The decrease in mechanical properties led to a significant decrease in flexural properties under normal temperature, wet and slippery and low temperature conditions, resulting in poorer durability.

[0141] Compared with Example 3, Comparative Example 4 showed a significant decrease in the dry / wet friction coefficient. The reason is that Comparative Example 4 used a polyether-modified siloxane without PO segments. The unbranched methyl groups provided hydrophobicity and had no synergistic effect with the ester-type plasticizer containing benzyl structures, resulting in a decrease in the dry / wet friction coefficient and a deterioration in anti-slip performance.

[0142] Compared with Example 3, Comparative Example 5 used the conventional plasticizer dioctyl maleate instead of the benzyl-containing ester plasticizer. Although the mechanical properties did not change much and the room temperature flexural strength remained basically unchanged, the number of flexural cycles and the dry / wet friction coefficient decreased significantly under wet conditions. The reason is that the benzyl-containing ester plasticizer, with its unique molecular structure and steric hindrance effect, can reduce the hydrolysis rate of ester bonds, delay water molecule penetration, and improve durability in wet environments. The combination of the benzyl structure and the cyclohexane structure can improve the low-temperature flexural strength of the sole, making the sole less prone to cracking in cold environments and improving the durability of the sole in cold environments.

[0143] In summary, the shoe soles made from the high anti-slip and durable polyurethane resin prepared by this invention have a molding density of 800-835 kg / m³. 3 It exhibits excellent mechanical properties, especially under wet and low-temperature conditions, demonstrating superior durability. It also boasts excellent dry / wet friction coefficients, providing good anti-slip effects and meeting safety standards while remaining durable.

Claims

1. A polyurethane microporous resin for shoe soles with high anti-slip and durability, characterized in that, It is composed of component A and component B in a mass ratio of 100:(60-90). Component A includes the following raw materials in parts by mass: Polyester polyol a: 70-90 parts; Polyester polyol b: 5-20 parts; Polyether polyol: 5-10 parts; Chain extender: 5-10 parts; Foaming agent: 0.3-0.6 parts; Catalyst: 0.6-1.5 parts; Foaming agent: 0.2-0.5 parts; Polyether-modified siloxane: 0.3-0.8 parts; Ester-type plasticizers containing benzyl groups: 5-10 parts; In component A, the sum of the mass fractions of polyester polyol a, polyester polyol b, and polyether polyol is 100 parts. Component B comprises the following raw materials in parts by weight: Polyester polyol a: 10-20 parts; Polyester polyol b: 5-10 parts; Polyether polyol: 5-10 parts; Ester-type plasticizers containing benzyl groups: 5-10 parts; Isocyanate: 55-70 parts; The polyester polyol a is prepared by polycondensation reaction of difunctional small molecule polyol a and adipic acid, with a functionality of 2 and a number-average molecular weight of 3000-4000 g / mol. The polyester polyol b is prepared by polycondensation reaction of a mixture of difunctional small molecule polyol b and trifunctional small molecule polyol c with adipic acid, with a functionality >2 and a number average molecular weight of 1200-2000 g / mol. The polyether polyol has a functionality of 2-3, a number-average molecular weight of 4000-6000 g / mol, and a primary hydroxyl content >70%. The polyether-modified siloxane is prepared by an addition reaction of hydrogen-containing siloxane and EO, PO copolyallyl-terminated polyether. The number average molecular weight of the EO, PO copolyallyl-terminated polyether is 1400-1500 g / mol, and the number average molecular weight of the polyether-modified siloxane is 1700 g-2700 g / mol.

2. The high anti-slip and durable polyurethane microporous shoe sole resin according to claim 1, characterized in that, Small molecule polyol a is one of ethylene glycol, diethylene glycol, and 1,4-butanediol; small molecule polyol b is one of ethylene glycol and diethylene glycol; and small molecule polyol c is one of glycerol and trimethylolpropane.

3. The high anti-slip and durable polyurethane microporous shoe sole resin according to claim 1, characterized in that, The chain extender is one or two of ethylene glycol, diethylene glycol, and 1,4-butanediol.

4. The high anti-slip and durable polyurethane microporous shoe sole resin according to claim 1, characterized in that, The foaming agent is a polysiloxane-olefin oxide block copolymer.

5. The high anti-slip and durable polyurethane microporous shoe sole resin according to claim 1, characterized in that, The catalyst is a tertiary amine catalyst, and the foaming agent is water.

6. The high anti-slip and durable polyurethane microporous shoe sole resin according to claim 1, characterized in that, The ester-type plasticizer containing a benzyl group is butylbenzylcyclohexane-1,2-dicarboxylic acid ester, with the following molecular structural formula: 。 7. The high anti-slip and durable polyurethane microporous shoe sole resin according to claim 1, characterized in that, The specific preparation method of the polyether-modified siloxane is as follows: add hydrogen-containing siloxane and EO, PO copolyallyl-terminated polyether to a reactor at a molar ratio of 1.0:(1.0-2.0), add 30 ppm of alkynyl inhibitor and 15 ppm of platinum catalyst (based on the total weight of the reactants), heat to 100-110℃, and react for 3-5 hours to obtain the polyether-modified siloxane.

8. The high anti-slip and durable polyurethane microporous shoe sole resin according to claim 1, characterized in that, The isocyanate is a mixture of 4,4-diphenylmethane diisocyanate and carbodiimide-modified isocyanate.

9. A method for preparing a high-slip-resistant and durable polyurethane microporous shoe sole resin according to any one of claims 1-8, characterized in that, Includes the following steps: (1) Preparation of component A: Polyester polyol a, polyester polyol b, polyether polyol, chain extender, foam leveler, catalyst, foaming agent, polyether modified siloxane, and ester plasticizer containing benzyl structure are added into the reactor and stirred at 40-60℃ for 1-2 hours to obtain component A. (2) Preparation of component B: Polyester polyol a, polyester polyol b, polyether polyol and ester plasticizer containing benzyl structure are put into the reactor, the material temperature is controlled at 40-50℃, isocyanate is added, and after reacting at 70-80℃ for 2-3h, component B with -NCO content of 16.9-22.6wt.% is obtained.

10. The application of a high-slip-resistant and durable polyurethane microporous shoe sole resin according to any one of claims 1-8, characterized in that, For the preparation of polyurethane microporous shoe soles, the preparation method is as follows: Component A and Component B are injected into the material tank of a low-pressure casting machine, and Component A and Component B are mixed at a mass ratio of 100:(60-90). The mixture is then injected into a mold at 45-60℃ and the mold is opened after 2-4 minutes to obtain a polyurethane microporous shoe sole with high anti-slip durability.

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