Yellowing-resistant transparent polyurethane sole material capable of reducing noise and preparation method of yellowing-resistant transparent polyurethane sole material

Abstract

The invention belongs to the technical field of polyurethane, and particularly relates to a yellowing-resistant transparent polyurethane sole material capable of reducing noise and a preparation method of the yellowing-resistant transparent polyurethane sole material. The invention discloses a composite chain extender, which is prepared from the following components in parts by mass: 100 parts of a composite chain extender component P and 68 to 121 parts of a polyurethane prepolymer component I. The composite chain extender component P is prepared from the following raw materials in parts by mass: 88.4 to 91.5 parts of polyester polyol A, 7 to 10 parts of micromolecular polyol, 0.2 to 0.4 part of an antioxidant, 0.2 to 0.4 part of an ultraviolet light absorber and 0.8 to 1 part of a catalyst. The polyurethane prepolymer component I is prepared from the following raw materials in parts by mass: 49 to 62 parts of polyester polyol B, 36.9 to 50.1 parts of isocyanate, 0.3 to 0.5 part of double-end single hydroxyl organic silicon and 0.6 part of an antioxidant. The prepared CPU shoe outsole is small in abnormal sound generated in the walking process, high in wear resistance, transparent and resistant to yellowing.

Description

Technical Field

[0001] This invention belongs to the field of polyurethane technology, specifically relating to a noise-reducing, yellowing-resistant, transparent polyurethane shoe sole material and its preparation method. Background Technology

[0002] Polyurethane (PU) is a polymer material formed by the condensation reaction of polyols and polyisocyanates. It possesses excellent mechanical properties, good wear resistance, and superior processing performance. Its applications are wide-ranging, including polyurethane plastics, fibers, rubber, and elastomers. In shoe outsoles, polyurethane elastomers are primarily used in the footwear industry. They are oil-resistant, wear-resistant, low-temperature resistant, and aging-resistant, making them suitable for various sports shoes and everyday footwear. PU has become an ideal material for manufacturing high-quality shoe outsoles. While using polyurethane (CPU) to produce shoe outsoles offers both economic and social benefits, its high elasticity can cause a squeaking sound similar to that of a squeezed sponge during walking due to bending and stretching. This drawback necessitates further noise reduction requirements for future shoe outsole development.

[0003] Currently, the diisocyanates used in the footwear industry mainly employ aromatic diisocyanates with benzene ring structures as the primary raw material. Due to the introduction of benzene rings into the molecular structure, polyurethane-type automotive leather, bag leather, and shoe leather exhibit good thermal stability, are simple to process, and are inexpensive. However, polyurethane-type footwear materials prepared using diisocyanates with benzene ring structures are prone to yellowing. While the alkyd polycondensation activity during the synthesis of ordinary aliphatic diisocyanates and aliphatic polyester polyols is relatively high, the resulting footwear materials have relatively weak strength and cannot adequately meet the market's demand for high-performance products.

[0004] Chinese invention patent application publication number CN110467713A discloses a thermoplastic organosilicon polyurethane elastomer material and its preparation method. It uses terminal hydroxyl alkyl siloxane compounds for in-situ synthesis within the thermoplastic polyurethane elastomer material, introducing organosilicon components. This results in a smooth surface and good feel in the product, improving its elasticity, mechanical properties, abrasion resistance, and low-temperature resistance. Simultaneously, the addition of a coupling agent improves the compatibility between the organosilicon and the thermoplastic elastomer, preventing delamination and performance degradation due to uneven mixing. However, it does not mention that the elastomer maintains good transparency after the addition of the organosilicon component, a crucial factor particularly important in footwear materials. Furthermore, data from Example 2 and Comparative Example 1 of this patent show that the abrasion resistance increases from 75mm after the introduction of organosilicon and coupling agent components. 3 Reduced to 45mm 3 It decreased by 40%, and there is still room for the decline to increase. Summary of the Invention

[0005] To address the aforementioned technical problems, this invention provides a noise-reducing, yellowing-resistant, transparent polyurethane sole material. The resulting CPU shoe outsole exhibits low noise during walking, high wear resistance, and is transparent and resistant to yellowing. This invention also provides a method for its preparation.

[0006] The noise-reducing, yellowing-resistant, transparent polyurethane shoe sole material of this invention comprises the following components by weight: Component P of the composite chain extender, 100 parts. Polyurethane prepolymer component I, 68-121 parts, The composite chain extender P component comprises the following raw materials in parts by mass: Polyester polyol A, 88.4-91.5 parts, Small molecule polyols, 7-10 parts Antioxidant, 0.2-0.4 parts, Ultraviolet absorber, 0.2-0.4 parts, Catalyst, 0.8-1 part; The small molecule polyol is at least one of ethylene glycol, 1,4-butanediol or 1,6-hexanediol; the polyester polyol A is an ethylene glycol-butanediol-adipic acid (EG, BG / AA) series polyester polyol with a number average molecular weight of 1000, 2000 or 3000, preferably PE-2410 (number average molecular weight 1000), PE-2420 (number average molecular weight 2000) or PE-2430 (number average molecular weight 3000) from Shandong Yinuowei Polyurethane Co., Ltd.

[0007] The polyurethane prepolymer component I comprises the following raw materials in parts by weight: Polyester polyol B, 49-62 parts, Isocyanate, 36.9-50.1 parts, Bi-terminated monohydroxy organosilicon, 0.3-0.5 parts. Antioxidant, 0.6 parts; Polyester polyol B is a series of polyester polyols consisting of ethylene glycol-methylpropylene glycol-adipic acid-isophthalic acid (EG, MPO / AA, IPA), with a number average molecular weight of 1000, 1500 or 2000.

[0008] Preferably, the preparation method of polyester polyol B is as follows: Ethylene glycol, methyl propylene glycol, adipic acid and isophthalic acid are added to a reaction vessel in a mass ratio of 100:36:(140-153):(107-116), stirring is started, and water begins to be discharged when the temperature rises to 140-145℃. The reflux temperature is controlled at 105-110℃, and then the temperature is gradually increased to 230-250℃. Vacuum is gradually drawn until the required number average molecular weight and water content ≤0.05% are obtained. Then the temperature is lowered to obtain the product.

[0009] Preferably, the antioxidant is at least one of antioxidant 1076 and antioxidant 1010.

[0010] Preferably, the ultraviolet absorber is at least one of ultraviolet absorbers UV-1 and UV-531.

[0011] Preferably, the catalyst is at least one of the amine catalyst DXD-06C and the zinc-bismuth composite catalyst BX-EM23.

[0012] Preferably, the isocyanate is at least one of phenyl dimethyl diisocyanate (XDI) and tetramethyl phenyl dimethyl diisocyanate (TMXDI).

[0013] Preferably, the dual-terminated monohydroxy organosilicon is at least one of 8814F4 and 8814F8.

[0014] The method for preparing the noise-reducing, yellowing-resistant, transparent polyurethane shoe sole material of the present invention includes the following steps: (1) Preparation of component P of the composite chain extender: Polyester polyol was added to a reactor, and a vacuum was drawn to ensure a vacuum degree of ≤-0.095MPa. The temperature was raised to 80℃ and stirred evenly. A sample was taken to test the moisture content. If the moisture content was ≤0.05%, an antioxidant and a UV absorber were added. The vacuum degree was drawn again to ensure a vacuum degree of ≤-0.095MPa, and the mixture was stirred for 30 minutes. The temperature of the material in the reactor was lowered to below 60℃, nitrogen was added to bring the pressure to atmospheric pressure, and small molecule polyol and catalyst were added. The mixture was stirred for another 30 minutes to obtain the composite chain extender component P. (2) Preparation of component I of polyurethane prepolymer: Polyester polyol B was tested for moisture content ≤0.05%. Polyester polyol B and double-terminated monohydroxy organosilicon were added to a reactor, and stirring was started. At the same time, circulating cooling water was turned on to cool the reactor to below 40℃. Isocyanate at a temperature below 55℃ was added to the reactor. After the addition was completed, the reactor was first sealed with nitrogen and a slight positive pressure was maintained inside the reactor. The mixture was stirred for 30 minutes. The temperature was raised to 75℃ in the first 1 hour and held for 2.5 hours. During the holding period, an antioxidant was added and the bubbles were removed until the vacuum degree was ≤-0.095MPa. Polyurethane prepolymer component I with an isocyanate content of 13.0%-15.0% was prepared. (3) Mix the composite chain extender P component and the polyurethane prepolymer I component at a mass ratio of 100:(68-121) at 60°C until uniform, then pour the mixture into a mold that has been preheated to 80°C. Press the gel point and heat to cure the mixture.

[0015] Compared with the prior art, the beneficial effects of the present invention are: 1. This invention starts from the principle of noise generation and reduces the vibration generated during the system's movement by reducing the impact rebound of the system, thereby achieving the effect of noise reduction. By introducing polyester polyol B with short-chain small molecule alcohol, side methyl small molecule alcohol and rigid isophthalic acid structure, the impact rebound is effectively reduced, achieving the ideal noise reduction effect. 2. By introducing reactive double-terminated monohydroxy organosilicon into the prepolymer, the system can still maintain excellent transparency by participating in the chemical reaction, which can greatly reduce the wear of the system without affecting the transparency effect. 3. The present invention uses an aliphatic isocyanate containing a benzene ring in its system structure, which has advantages in mechanical properties compared with ordinary aliphatic materials in addition to being resistant to yellowing. Detailed Implementation

[0016] The technical solution of the present invention will be clearly and completely described below with reference to the embodiments.

[0017] Unless otherwise specified, all raw materials used in the examples and comparative examples were commercially available. Some raw material descriptions are as follows: PE-2410, Polyester Polyol A, Number Average Molecular Weight 1000, Shandong Yinuowei Polyurethane Co., Ltd.; PE-2420, Polyester Polyol A, Number Average Molecular Weight 2000, Shandong Yinuowei Polyurethane Co., Ltd.; PE-2430, Polyester Polyol A, Number Average Molecular Weight 3000, Shandong Yinuowei Polyurethane Co., Ltd.; PE-4010, Butylene glycol-adipic acid (BG / AA) series polyester polyol, number average molecular weight 1000, Shandong Yinuowei Polyurethane Co., Ltd. PE-2320, ethylene glycol-propylene glycol-adipic acid (EG, PG / AA) series polyester polyol, number average molecular weight 1000, Shandong Yinuowei Polyurethane Co., Ltd.; Phenylem diisocyanate, Wanhua Chemical Group Co., Ltd.; Tetramethylphenyldimethyl diisocyanate, Shanghai Puzhan Industrial Co., Ltd.; Amine catalyst DXD-06C, Shandong Yinuowei Polyurethane Co., Ltd.; Zinc-bismuth composite catalyst BX-EM23, Guangzhou Yourun Synthetic Materials Co., Ltd.; 8814F4, number average molecular weight 4500, Guangzhou Sloco New Materials Co., Ltd.; 8814F8, number average molecular weight 6000, Guangzhou Sloco New Materials Co., Ltd.; Wear-resistant agent CUBD-NM01, Guangzhou Yourun Synthetic Materials Co., Ltd.; Polyester polyol B with a number average molecular weight of 1000 is prepared as follows: Ethylene glycol, methyl propylene glycol, adipic acid, and isophthalic acid are added to a reaction vessel in a mass ratio of 100:36:140:107. Stirring is started, and water begins to be released when the temperature rises to 140℃. The reflux temperature is controlled at 110℃, and then the temperature is gradually increased to 240℃. Vacuum is gradually drawn until the number average molecular weight is 1000 and the moisture content is ≤0.05%. The product is then cooled to obtain the final product.

[0018] Polyester polyol B with a number average molecular weight of 1500 is prepared as follows: Ethylene glycol, methyl propylene glycol, adipic acid, and isophthalic acid are added to a reaction vessel in a mass ratio of 100:36:149:113. Stirring is started, and water begins to be released when the temperature rises to 145°C. The reflux temperature is controlled at 105°C, and then the temperature is gradually increased to 230°C. Vacuum is gradually drawn until the number average molecular weight is 1500 and the moisture content is ≤0.05%. The product is then cooled to obtain the final product.

[0019] Polyester polyol B with a number average molecular weight of 2000 is prepared as follows: Ethylene glycol, methyl propylene glycol, adipic acid, and isophthalic acid are added to a reaction vessel in a mass ratio of 100:36:153:116. Stirring is started, and water begins to be released when the temperature reaches 143°C. The reflux temperature is controlled at 108°C, and then the temperature is gradually increased to 250°C. Vacuum is gradually drawn until the number average molecular weight is 2000 and the moisture content is ≤0.05%. The product is then cooled to obtain the final product.

[0020] Example 1 The noise-reducing, yellowing-resistant, transparent polyurethane sole material is composed of composite chain extender component P and polyurethane prepolymer component I in a mass ratio of 100:116. The composite chain extender P component comprises the following raw materials in parts by mass: Polyester polyol A, PE-2410, 90.7 parts. 8 parts of the small molecule polyol 1,4-butanediol. Antioxidant 1076, 0.3 parts. UV absorber UV-1, 0.1 parts, UV absorber UV-531, 0.1 parts. Amine catalyst DXD-06C, 0.8 parts; The polyurethane prepolymer component I comprises the following raw materials in parts by weight: Polyester polyol B (number average molecular weight 1500), 62 parts, Phthalic diisocyanate, 36.9 parts Double-terminated monohydroxy organosilicon 8814F4, 0.5 parts. Antioxidant 1010, 0.6 parts; The method for preparing the noise-reducing, yellowing-resistant, transparent polyurethane shoe sole material includes the following steps: (1) Preparation of component P of the composite chain extender: Polyester polyol A (PE-2410) was added to a reactor, and a vacuum was drawn to ensure a vacuum degree of ≤-0.095MPa. The temperature was raised to 80℃ and stirred evenly. A sample was taken to test the moisture content. After the moisture content was ≤0.05%, antioxidant 1076, ultraviolet absorber UV-1, and UV-531 were added. The vacuum degree was drawn to ensure a vacuum degree of ≤-0.095MPa and stirred for 30 minutes. The temperature of the material in the reactor was lowered to below 60℃, nitrogen was added to bring the pressure to normal, and small molecule polyol 1,4-butanediol and amine catalyst DXD-06C were added. The mixture was stirred for another 30 minutes to obtain the composite chain extender component P.

[0021] (2) Preparation of component I of polyurethane prepolymer: Polyester polyol B with a moisture content ≤0.05% was tested. Polyester polyol B with a number average molecular weight of 1500 and double-terminated monohydroxyl organosilicon 8814F4 were added to the reactor, and stirring was started. At the same time, the circulating cooling water was turned on to cool the reactor to below 40℃. Phenylene diisocyanate with a temperature below 55℃ was added to the reactor. After the addition was completed, the reactor was first sealed with nitrogen and a slight positive pressure was maintained inside the reactor. The mixture was stirred for 30 minutes. The temperature was raised to 75℃ in the first 1 hour and held for 2.5 hours. During the holding period, antioxidant 1010 was added and the bubbles were removed until the vacuum degree was ≤-0.095MPa. Polyurethane prepolymer component I with an isocyanate content of 13.0% was prepared. (3) Mix the composite chain extender P component and the polyurethane prepolymer I component at a mass ratio of 100:116 at 60°C until uniform, then pour the mixture into a mold that has been preheated to 80°C. Press the gel point and heat to cure the mixture.

[0022] Example 2 The noise-reducing, yellowing-resistant, transparent polyurethane sole material is composed of composite chain extender component P and polyurethane prepolymer component I in a mass ratio of 100:75. The composite chain extender P component comprises the following raw materials in parts by mass: Polyester polyol A, PE-2420, 88.4 parts, 10 parts of small molecule polyol 1,6-hexanediol. Antioxidant 1010, 0.1 parts, Antioxidant 1076, 0.2 parts, UV absorber UV-531, 0.3 parts, Zinc-bismuth composite catalyst BX-EM23, 1 part; The polyurethane prepolymer component I comprises the following raw materials in parts by weight: Polyester polyol B (number average molecular weight 1000), 56.1 parts. Phthalic diisocyanate, 42.9 parts Double-terminated monohydroxy organosilicon 8814F4, 0.17 parts. Double-terminated monohydroxy organosilicon 8814F8, 0.23 parts. Antioxidant 1076, 0.6 parts; The method for preparing the noise-reducing, yellowing-resistant, transparent polyurethane shoe sole material includes the following steps: (1) Preparation of component P of the composite chain extender: Polyester polyol A (PE-2420) was added to a reactor, and a vacuum was drawn to ensure a vacuum degree of ≤-0.095MPa. The temperature was raised to 80℃ and stirred evenly. A sample was taken to test the moisture content. After the moisture content was ≤0.05%, antioxidants 1010 and 1076 and ultraviolet absorber UV-531 were added. The vacuum degree was drawn to ensure a vacuum degree of ≤-0.095MPa and stirred for 30 minutes. The temperature of the material in the reactor was lowered to below 60℃, nitrogen was added to bring the pressure to normal, and small molecule polyol 1,6-hexanediol and zinc bismuth composite catalyst BX-EM23 were added. The mixture was stirred for another 30 minutes to obtain the composite chain extender component P.

[0023] (2) Preparation of component I of polyurethane prepolymer: Polyester polyol B with a moisture content ≤0.05% was tested. Polyester polyol B with a number average molecular weight of 1000 and dual-terminated monohydroxy organosilicon 8814F4 and 8814F8 were added to the reactor, and the stirring was turned on. At the same time, the circulating cooling water was turned on to cool the reactor to below 40°C. Then, phthalimide diisocyanate with a temperature below 55°C was added to the reactor. After the addition was completed, the reactor was first sealed with nitrogen and a slight positive pressure was maintained inside the reactor. The mixture was stirred for 30 minutes. The temperature was raised to 75°C in the first 1 hour and held for 2.5 hours. During the holding period, antioxidant 1076 was added and the bubbles were removed until the vacuum degree was ≤-0.095MPa. Polyurethane prepolymer component I with an isocyanate content of 14.4% was prepared. (3) Mix the composite chain extender component P and the polyurethane prepolymer component I at a mass ratio of 100:75 at 60°C until uniform, then pour the mixture into a mold that has been preheated to 80°C. Press the gel point and heat to cure the mixture.

[0024] Example 3 The noise-reducing, yellowing-resistant, transparent polyurethane sole material is composed of composite chain extender component P and polyurethane prepolymer component I in a mass ratio of 100:108. The composite chain extender P component comprises the following raw materials in parts by mass: Polyester polyol A, PE-2410, 50 parts Polyester polyol A, PE-2430, 41.4 parts. Small molecule polyol ethylene glycol, 7 parts Antioxidant 1076, 0.4 parts. UV absorber UV-1, 0.3 parts, Zinc-bismuth composite catalyst BX-EM23, 0.9 parts; The polyurethane prepolymer component I comprises the following raw materials in parts by weight: Polyester polyol B (number average molecular weight 1000), 15.3 parts. Polyester polyol B (number average molecular weight 2000), 35.5 parts. Tetramethylphenyl dimethylene diisocyanate, 48.3 parts Double-terminated monohydroxy organosilicon 8814F8, 0.3 parts. Antioxidant 1076, 0.6 parts; The method for preparing the noise-reducing, yellowing-resistant, transparent polyurethane shoe sole material includes the following steps: (1) Preparation of component P of the composite chain extender: Polyester polyols A (PE-2410) and PE-2430 were added to a reactor, and a vacuum was drawn to ensure a vacuum degree of ≤-0.095MPa. The temperature was raised to 80℃ and stirred evenly. A sample was taken to test the moisture content. After the moisture content was ≤0.05%, antioxidant 1076 and ultraviolet absorber UV-1 were added. A vacuum was drawn to ensure a vacuum degree of ≤-0.095MPa and stirred for 30 minutes. The temperature of the material in the reactor was lowered to below 60℃, nitrogen was added to bring the pressure to normal, and small molecule polyol ethylene glycol and zinc bismuth composite catalyst BX-EM23 were added. The mixture was stirred for another 30 minutes to obtain the composite chain extender component P.

[0025] (2) Preparation of component I of polyurethane prepolymer: Polyester polyol B with a moisture content ≤0.05% was tested. Polyester polyol B with a number average molecular weight of 1000 and 2000 and double-terminated monohydroxy organosilicon 8814F8 were added to the reactor, and the stirring was turned on. At the same time, the circulating cooling water was turned on to cool the reactor to below 40°C. Tetramethylphenyl dimethylene diisocyanate with a temperature below 55°C was added to the reactor. After the addition was completed, the reactor was first sealed with nitrogen and a slight positive pressure was maintained inside the reactor. The mixture was stirred for 30 minutes. The temperature was raised to 75°C in the first 1 hour and held for 2.5 hours. During the holding period, antioxidant 1076 was added and the bubbles were removed until the vacuum degree was ≤-0.095MPa. Polyurethane prepolymer component I with an isocyanate content of 13.8% was prepared. (3) Mix the composite chain extender P component and the polyurethane prepolymer I component at a mass ratio of 100:108 at 60°C until uniform, then pour the mixture into a mold that has been preheated to 80°C. Press the gel point and heat to cure the mixture.

[0026] Example 4 The noise-reducing, yellowing-resistant, transparent polyurethane sole material is composed of composite chain extender component P and polyurethane prepolymer component I in a mass ratio of 100:68. The composite chain extender P component comprises the following raw materials in parts by mass: Polyester polyol A, PE-2430, 89.5 parts. 1,4-Butanediol, a small molecule polyol, 6 parts. Small molecule polyol 1,6-hexanediol, 3 parts Antioxidant 1010, 0.3 parts, UV absorber UV-1, 0.4 parts, Zinc-bismuth composite catalyst BX-EM23, 0.5 parts, Amine catalyst DXD-06C, 0.3 parts; The polyurethane prepolymer component I comprises the following raw materials in parts by weight: Polyester polyol B (number average molecular weight 2000), 56.1 parts. Tetramethylphenyl dimethylene diisocyanate, 17.1 parts, Phthalic dimethyl diisocyanate, 25.7 parts, Double-terminated monohydroxy organosilicon 8814F4, 0.5 parts. Antioxidant 1010, 0.6 parts; The method for preparing the noise-reducing, yellowing-resistant, transparent polyurethane shoe sole material includes the following steps: (1) Preparation of component P of the composite chain extender: Polyester polyol A (PE-2430) was added to a reactor, and a vacuum was drawn to ensure a vacuum degree of ≤-0.095MPa. The temperature was raised to 80℃ and stirred evenly. A sample was taken to test the moisture content. After the moisture content was ≤0.05%, antioxidant 1010 and ultraviolet absorber UV-1 were added. The vacuum degree was drawn to ensure a vacuum degree of ≤-0.095MPa and stirred for 30 minutes. The temperature of the material in the reactor was lowered to below 60℃, nitrogen was added to bring the pressure to normal, and small molecule polyols 1,4-butanediol, 1,6-hexanediol, zinc bismuth composite catalyst BX-EM23, and amine catalyst DXD-06C were added. The mixture was stirred for another 30 minutes to obtain the composite chain extender component P.

[0027] (2) Preparation of component I of polyurethane prepolymer: Polyester polyol B with a moisture content ≤0.05% was tested. Polyester polyol B with a number average molecular weight of 2000 and double-terminated monohydroxy organosilicon 8814F4 were added to the reactor, and stirring was started. At the same time, the circulating cooling water was turned on to cool the reactor to below 40℃. Tetramethyl phthalimide diisocyanate and phthalimide diisocyanate with a temperature below 55℃ were added to the reactor. After the materials were added, the reactor was first sealed with nitrogen and a slight positive pressure was maintained inside the reactor. The mixture was stirred for 30 minutes. The temperature was raised to 75℃ in the first 1 hour and held for 2.5 hours. During the holding period, antioxidant 1010 was added and the bubbles were removed until the vacuum degree was ≤-0.095MPa. Polyurethane prepolymer component I with an isocyanate content of 15.0% was prepared. (3) Mix the composite chain extender P component and the polyurethane prepolymer I component at a mass ratio of 100:68 at 60°C until uniform, then pour the mixture into a mold that has been preheated to 80°C. Press the gel point and heat to cure the mixture.

[0028] Example 5 The noise-reducing, yellowing-resistant, transparent polyurethane sole material is composed of composite chain extender component P and polyurethane prepolymer component I in a mass ratio of 100:121. The composite chain extender P component comprises the following raw materials in parts by mass: Polyester polyol A, PE-2410, 91.5 parts. Small molecule polyol ethylene glycol, 7 parts Antioxidant 1076, 0.2 parts, UV absorber UV-1, 0.3 parts, UV absorber UV-531, 0.1 parts. Zinc-bismuth composite catalyst BX-EM23, 0.9 parts; The polyurethane prepolymer component I comprises the following raw materials in parts by weight: Polyester polyol B (number average molecular weight 1000), 10 parts. Polyester polyol B (number average molecular weight 1500), 39 parts. Tetramethylphenyl dimethylene diisocyanate, 50.1 parts Double-terminated monohydroxy organosilicon 8814F4, 0.3 parts. Antioxidant 1010, 0.6 parts; The method for preparing the noise-reducing, yellowing-resistant, transparent polyurethane shoe sole material includes the following steps: (1) Preparation of component P of the composite chain extender: Polyester polyol A (PE-2410) was added to a reactor, and a vacuum was drawn to ensure a vacuum degree of ≤-0.095MPa. The temperature was raised to 80℃ and stirred evenly. A sample was taken to test the moisture content. After the moisture content was ≤0.05%, antioxidant 1076, ultraviolet absorber UV-1, and UV-531 were added. The vacuum degree was drawn to ensure a vacuum degree of ≤-0.095MPa and stirred for 30 minutes. The temperature of the material in the reactor was lowered to below 60℃, nitrogen was added to bring the pressure to normal, and small molecule polyol ethylene glycol and zinc bismuth composite catalyst BX-EM23 were added. The mixture was stirred for another 30 minutes to obtain the composite chain extender component P.

[0029] (2) Preparation of component I of polyurethane prepolymer: Polyester polyol B with a moisture content ≤0.05% was tested. Polyester polyol B with a number average molecular weight of 1000 and 1500 and dual-terminated monohydroxy organosilicon 8814F4 were added to the reactor, and the stirring was turned on. At the same time, the circulating cooling water was turned on to cool the reactor to below 40°C. Tetramethylphenyl dimethylene diisocyanate with a temperature below 55°C was added to the reactor. After the addition was completed, the reactor was first sealed with nitrogen and a slight positive pressure was maintained inside the reactor. The mixture was stirred for 30 minutes. The temperature was raised to 75°C in the first 1 hour and held for 2.5 hours. During the holding period, antioxidant 1010 was added and the bubbles were removed until the vacuum degree was ≤-0.095MPa. Polyurethane prepolymer component I with an isocyanate content of 14.2% was prepared. (3) Mix the composite chain extender P component and the polyurethane prepolymer I component at a mass ratio of 100:121 at 60°C until uniform, then pour the mixture into a mold that has been preheated to 80°C. Press the gel point and heat to cure the mixture.

[0030] Comparative Example 1 The only difference between Comparative Example 1 and Example 1 is that the polyester polyol A (PE-2410) with a number average molecular weight of 1000 is replaced by an equal mass of polyester polyol PE-4010 with a number average molecular weight of 1000.

[0031] Comparative Example 2 The only difference between Comparative Example 2 and Example 1 is that polyester polyol A (PE-2410) with a number average molecular weight of 1000 is replaced by an equal mass of polyester polyol B with a number average molecular weight of 1000.

[0032] Comparative Example 3 The only difference between Comparative Example 3 and Example 4 is that the polyester polyol B with a number average molecular weight of 2000 is replaced by an equal mass of polyester polyol PE-2320 with a number average molecular weight of 2000.

[0033] Comparative Example 4 The only difference between Comparative Example 4 and Example 4 is that the polyurethane prepolymer I component in Comparative Example 4 includes the following raw materials: Polyester polyol B (number average molecular weight 2000), 46.2 parts. 4,4'-Dicyclohexylmethane diisocyanate (HMDI), 52.8 parts, Double-terminated monohydroxy organosilicon 8814F4, 0.5 parts. Antioxidant 1010, 0.6 parts.

[0034] Comparative Example 5 The only difference between Comparative Example 5 and Example 4 is that the polyurethane prepolymer I component in Comparative Example 5 includes the following raw materials: Polyester polyol B (number average molecular weight 2000), 46.5 parts. Diphenylmethane diisocyanate, 36.7 parts, Carbodiimide-modified MDI, 15.8 parts, Double-terminated monohydroxy organosilicon 8814F4, 0.4 parts. Antioxidant 1010, 0.6 parts.

[0035] Comparative Example 6 The noise-reducing, yellowing-resistant, transparent polyurethane sole material is composed of composite chain extender component P and polyurethane prepolymer component I in a mass ratio of 100:121. The composite chain extender P component comprises the following raw materials in parts by mass: Polyester polyol A, PE-2410, 91.5 parts. Small molecule polyol ethylene glycol, 7 parts Antioxidant 1076, 0.2 parts, UV absorber UV-1, 0.3 parts, UV absorber UV-531, 0.1 parts. Zinc-bismuth composite catalyst BX-EM23, 0.9 parts; The polyurethane prepolymer component I comprises the following raw materials in parts by weight: Polyester polyol B (number average molecular weight 1000), 9.8 parts. Polyester polyol B (number average molecular weight 1500), 39.2 parts. Tetramethylphenyl dimethylene diisocyanate, 50.1 parts Wear-resistant agent CUBD-NM01, 0.3 parts, Antioxidant 1010, 0.6 parts; The method for preparing the noise-reducing, yellowing-resistant, transparent polyurethane shoe sole material includes the following steps: (1) Preparation of component P of the composite chain extender: Polyester polyol A (PE-2410) was added to a reactor, and a vacuum was drawn to ensure a vacuum degree of ≤-0.095MPa. The temperature was raised to 80℃ and stirred evenly. A sample was taken to test the moisture content. After the moisture content was ≤0.05%, antioxidant 1076, ultraviolet absorber UV-1, and UV-531 were added. The vacuum degree was drawn to ensure a vacuum degree of ≤-0.095MPa and stirred for 30 minutes. The temperature of the material in the reactor was lowered to below 60℃, nitrogen was added to bring the pressure to normal, and small molecule polyol ethylene glycol and zinc bismuth composite catalyst BX-EM23 were added. The mixture was stirred for another 30 minutes to obtain the composite chain extender component P.

[0036] (2) Preparation of component I of polyurethane prepolymer: Polyester polyol B with a moisture content ≤0.05% was tested. Polyester polyol B with a number average molecular weight of 1000 and 1500 and wear-resistant agent CUBD-NM01 were added to the reactor, and stirring was started. At the same time, the circulating cooling water was turned on to cool the reactor to below 40℃. Tetramethylphenyl dimethylene diisocyanate with a temperature below 55℃ was added to the reactor. After the addition was completed, the reactor was first sealed with nitrogen and a slight positive pressure was maintained inside the reactor. The mixture was stirred for 30 minutes. The temperature was raised to 75℃ in the first 1 hour and held for 2.5 hours. During the holding period, antioxidant 1010 was added and the bubbles were removed until the vacuum degree was ≤-0.095MPa. Polyurethane prepolymer component I with an isocyanate content of 14.2% was prepared. (3) Mix the composite chain extender P component and the polyurethane prepolymer I component at a mass ratio of 100:121 at 60°C until uniform, then pour the mixture into a mold that has been preheated to 80°C. Press the gel point and heat to cure the mixture.

[0037] Comparative Example 7 The noise-reducing, yellowing-resistant, transparent polyurethane sole material is composed of composite chain extender component P and polyurethane prepolymer component I in a mass ratio of 100:121. The composite chain extender P component comprises the following raw materials in parts by mass: Polyester polyol A, PE-2410, 91.5 parts. Small molecule polyol ethylene glycol, 7 parts Antioxidant 1076, 0.2 parts, UV absorber UV-1, 0.3 parts, UV absorber UV-531, 0.1 parts. Zinc-bismuth composite catalyst BX-EM23, 0.9 parts; The polyurethane prepolymer component I comprises the following raw materials in parts by weight: Polyester polyol B (number average molecular weight 1000), 9.9 parts. Polyester polyol B (number average molecular weight 1500), 39.4 parts. Tetramethylphenyl dimethylene diisocyanate, 50.1 parts Antioxidant 1010, 0.6 parts; The method for preparing the noise-reducing, yellowing-resistant, transparent polyurethane shoe sole material includes the following steps: (1) Preparation of component P of the composite chain extender: Polyester polyol A (PE-2410) was added to a reactor, and a vacuum was drawn to ensure a vacuum degree of ≤-0.095MPa. The temperature was raised to 80℃ and stirred evenly. A sample was taken to test the moisture content. After the moisture content was ≤0.05%, antioxidant 1076, ultraviolet absorber UV-1, and UV-531 were added. The vacuum degree was drawn to ensure a vacuum degree of ≤-0.095MPa and stirred for 30 minutes. The temperature of the material in the reactor was lowered to below 60℃, nitrogen was added to bring the pressure to normal, and small molecule polyol ethylene glycol and zinc bismuth composite catalyst BX-EM23 were added. The mixture was stirred for another 30 minutes to obtain the composite chain extender component P.

[0038] (2) Preparation of component I of polyurethane prepolymer: Polyester polyol B with a moisture content of ≤0.05% was tested. Polyester polyol B with a number average molecular weight of 1000 and 1500 was added to the reactor, and stirring was started. At the same time, the circulating cooling water was turned on to cool the reactor to below 40°C. Tetramethylphenyl dimethylene diisocyanate with a temperature below 55°C was added to the reactor. After the addition was completed, the reactor was first sealed with nitrogen and a slight positive pressure was maintained inside the reactor. The mixture was stirred for 30 minutes. The temperature was raised to 75°C in the first 1 hour and held for 2.5 hours. During the holding period, antioxidant 1010 was added and the bubbles were removed until the vacuum degree was ≤-0.095MPa. Polyurethane prepolymer component I with an isocyanate content of 14.2% was obtained. (3) Mix the composite chain extender P component and the polyurethane prepolymer I component at a mass ratio of 100:121 at 60°C until uniform, then pour the mixture into a mold that has been preheated to 80°C. Press the gel point and heat to cure the mixture.

[0039] Performance testing The performance test results of the examples and comparative examples are shown in Table 1 below.

[0040] Table 1 Performance Test Tables for Examples and Comparative Examples

[0041] A comparison of the performance data from Comparative Example 1 and Example 1 shows that EG and BG type polyester polyol PE-2410 has shorter chain segments compared to BG type polyester polyol PE-4010 elastomer, resulting in a higher ester group density in the elastomer structure. The shorter molecular chains lead to lower chain segment flexibility and a poorer ability to recover their original shape under external force, resulting in lower resilience. Using even shorter chain segments would increase the crystallinity of the polyol and worsen its processability. Comparative Example 2, by simultaneously introducing isophthalic acid-based polyester polyols into the composite chain extender P component and the polyurethane prepolymer I component, resulted in an elastomer product with an excessively rigid structure and overly dense molecular chain arrangement forming microcrystalline regions. This increased light scattering led to decreased transparency of the product system. The present invention introduces isophthalic acid B, which has adipic acid and a rigid benzene ring structure, resulting in an elastomer with stronger tensile and tear strength and lower impact resilience. The performance data of Comparative Example 3 and Example 4 show that if polyester polyol B is replaced with adipic acid series polyester polyol, the mechanical properties of the elastomer are significantly reduced, the resilience is enhanced, and the noise reduction effect is weakened.

[0042] Comparison of data from Comparative Examples 4-5 and Example 4 shows that the present invention uses a special isocyanate that introduces a methylene group (-CH2-) between the benzene ring and the isocyanate group (-NCO) in the selection of prepolymer components, which blocks the formation of conjugated quinone structure and has high reactivity and fast curing speed. This allows the system to maintain the excellent process and comprehensive mechanical properties of aromatic products, while also having the non-yellowing property of aliphatic products.

[0043] As can be seen from Comparative Example 6 and Example 5, conventional silicone wear-resistant agents can reduce the friction coefficient through their unique lubricity, thus achieving the effect of reducing wear. However, they usually have poor miscibility with polyurethane systems. In contrast, the present invention uses hydroxyl silicone oligomers that can replace part of the diols and react directly with -NCO, allowing them to fully dissolve in the system and maintain good transparency. Furthermore, as can be seen from Comparative Example 7 and Example 5, the addition of hydroxyl silicone oligomers reduces the wear value of the system by 67%, demonstrating significant beneficial effects.

Claims

1. A noise-reducing, yellowing-resistant, transparent polyurethane shoe sole material, characterized in that, By mass, it includes the following components: Component P of the composite chain extender, 100 parts. Polyurethane prepolymer component I, 68-121 parts, The composite chain extender P component comprises the following raw materials in parts by mass: Polyester polyol A, 88.4-91.5 parts, Small molecule polyols, 7-10 parts Antioxidant, 0.2-0.4 parts, Ultraviolet absorber, 0.2-0.4 parts, Catalyst, 0.8-1 part; The small molecule polyol is at least one of ethylene glycol, 1,4-butanediol, or 1,6-hexanediol; polyester polyol A is a series of polyester polyols in the ethylene glycol-butanediol-adipic acid category. The polyurethane prepolymer component I comprises the following raw materials in parts by weight: Polyester polyol B, 49-62 parts, Isocyanate, 36.9-50.1 parts, Bi-terminated monohydroxy organosilicon, 0.3-0.5 parts. Antioxidant, 0.6 parts; Polyester polyol B is a series of polyester polyols consisting of ethylene glycol-methylpropylene glycol-adipic acid-isophthalic acid.

2. The noise-reducing, yellowing-resistant transparent polyurethane sole material according to claim 1, characterized in that, The preparation method of polyester polyol B is as follows: Ethylene glycol, methyl propylene glycol, adipic acid and isophthalic acid are added to the reaction vessel in a mass ratio of 100:36:(140-153):(107-116), stirring is started, and water begins to be discharged when the temperature rises to 140-145℃. The reflux temperature is controlled at 105-110℃, and then the temperature is raised to 230-250℃. After vacuuming, the temperature is lowered to obtain the product.

3. The noise-reducing, yellowing-resistant transparent polyurethane sole material according to claim 1, characterized in that, The antioxidant is at least one of antioxidant 1076 and antioxidant 1010.

4. The noise-reducing, yellowing-resistant transparent polyurethane sole material according to claim 1, characterized in that, The ultraviolet absorber is at least one of ultraviolet absorbers UV-1 and UV-531.

5. The noise-reducing, yellowing-resistant transparent polyurethane sole material according to claim 1, characterized in that, The catalyst is at least one of amine catalysts and zinc-bismuth composite catalysts.

6. The noise-reducing, yellowing-resistant transparent polyurethane sole material according to claim 1, characterized in that, The isocyanate is at least one of phenylene diisocyanate and tetramethylphenylene diisocyanate.

7. The noise-reducing, yellowing-resistant transparent polyurethane sole material according to claim 1, characterized in that, The dual-terminated monohydroxy organosilicon is at least one of 8814F4 and 8814F8.

8. A method for preparing a noise-reducing, yellowing-resistant, transparent polyurethane shoe sole material according to any one of claims 1-7, characterized in that, Includes the following steps: (1) Preparation of component P of the composite chain extender: Polyester polyol A was added to a reactor, and a vacuum was drawn to ensure a vacuum degree of ≤-0.095MPa. The temperature was raised to 80℃ and stirred evenly. A sample was taken to test the moisture content. If the moisture content was ≤0.05%, an antioxidant and an ultraviolet absorber were added. The vacuum degree was drawn again to ensure a vacuum degree of ≤-0.095MPa, and the mixture was stirred for 30 minutes. The temperature of the material in the reactor was lowered to below 60℃, nitrogen was added to bring the pressure to atmospheric pressure, and small molecule polyol and catalyst were added. The mixture was stirred for another 30 minutes to obtain the composite chain extender component P. (2) Preparation of component I of polyurethane prepolymer: Polyester polyol B was tested for moisture content ≤0.05%. Polyester polyol B and double-terminated monohydroxy organosilicon were added to a reactor, and stirring was started. At the same time, circulating cooling water was turned on to cool the reactor to below 40℃. Isocyanate at a temperature below 55℃ was added to the reactor. After the addition was completed, the reactor was first sealed with nitrogen and a slight positive pressure was maintained inside. The mixture was stirred for 30 minutes. The temperature was raised to 75℃ in the first 1 hour and held for 2.5 hours. During the holding period, an antioxidant was added and the bubbles were removed until the vacuum degree was ≤-0.095MPa. Polyurethane prepolymer component I with an isocyanate content of 13.0%-15.0% was prepared. (3) Mix the composite chain extender P component and the polyurethane prepolymer I component at a mass ratio of 100:(68-121) at 60°C until uniform, then pour the mixture into a mold that has been preheated to 80°C. Press the gel point and heat to cure the mixture.

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