Yellowing-resistant polyurethane elastomer shoe outsole material and preparation method thereof

Abstract

The invention discloses a yellowing-resistant polyurethane elastomer shoe outsole material and a preparation method thereof, and relates to the technical field of polyurethane elastomers, including a composite chain extender P component and a polyurethane prepolymer I component with a mass ratio of 1: (0.95-1.34); the composite chain extender P component includes 77.39-83.89 parts of polytetramethylene ether glycol, 10-13 parts of small molecule polyols, 2-5 parts of long-chain high-carbon fatty alcohols, 2-5 parts of multifunctional polyether polyols, 0.2-0.4 parts of antioxidants, 0.2-0.4 parts of ultraviolet absorbers, 0.7-1 parts of catalysts, and 0.01-0.03 parts of silicon defoamers; the polyurethane prepolymer I component includes 32.1-62.3 parts of polytetramethylene ether glycol, 37.1-67.2 parts of aliphatic isocyanates, and 0.6-0.8 parts of antioxidants. The invention meets the market requirements for high-performance CPU shoe outsoles.

Description

Technical Field

[0001] The invention relates to the technical field of polyurethane elastomers, and in particular to a yellowing-resistant polyurethane elastomer shoe outsole material and a preparation method thereof. Background Art

[0002] The materials commonly used in the market for outsoles are mainly rubber, EVA, TPU and cast polyurethane (hereinafter referred to as CPU). CPU has excellent physical properties and processing properties. Using it to prepare outsoles has both good economic benefits and high social benefits, making it an ideal material for manufacturing quality outsoles. When CPU is used in outsoles, the main molding methods are: 1) Inject CPU into the mold and use a flat vulcanizer to pressurize to prepare CPU outsoles with different patterns (the entire outsole or part of the outsole); 2) Put fabric with rich color patterns in the mold in advance, inject CPU and pressurize to obtain a composite outsole of fabric and CPU; 3) Directly decompress and cast CPU on the treated EVA, TPU foam or Pebax foam midsole to form a composite sole.

[0003] At present, the key raw material diisocyanate used to prepare shoe outsoles is mainly diisocyanate with a benzene ring structure. Because the benzene ring is introduced into the molecular structure, the product has good thermal stability, simple processing and low price. However, the polyurethane shoe outsoles prepared by using diisocyanate with a benzene ring structure and polyester polyol have the problem of easy yellowing. From the perspective of environmental protection, the benzene ring in its structure is difficult to degrade after use and it is difficult to meet the requirements of green environmental protection materials. At present, high-end brand shoe outsoles have higher requirements for yellowing resistance.

[0004] CPU shoe outsole materials mainly include: polyether shoe outsole materials, polyether-polyester combined shoe outsole materials and ordinary polyester shoe outsole materials. Among them, ordinary polyester shoe outsole materials are not resistant to low temperature and hydrolysis, and are easy to slip due to high hardness in cold areas in winter, which cannot meet the market's requirements for low temperature resistance of shoe outsole products; conventional polyether-polyester shoe outsole materials are not transparent enough; polyether shoe outsole materials are not wear-resistant and have insufficient mechanical properties, which need further improvement. In addition, in recent years, the concept of lightweight has gradually been integrated into people's lives, and it is also a new trend in the development of shoe outsole products. In summary, there is an urgent need to develop a yellowing-resistant polyurethane elastomer shoe outsole material that meets lightweight requirements. Summary of the invention

[0005] The technical problem to be solved by the present invention is to overcome the deficiencies of the prior art, provide a yellowing-resistant polyurethane elastomer shoe outsole material and a preparation method thereof, and meet the market performance requirements for low temperature resistance, yellowing resistance, high wear resistance and high tear performance CPU shoe outsole.

[0006] The technical solution of the present invention is:

[0007] In one aspect, the present invention provides a yellowing-resistant polyurethane elastomer shoe outsole material, comprising a composite chain extender component P and a polyurethane prepolymer component I in a mass ratio of 1:(0.95-1.34);

[0008] Wherein, the composite chain extender P component includes the following components in parts by weight:

[0009] Polytetramethylene ether glycol 77.39-83.89 parts

[0010] 10-13 parts of small molecule polyol

[0011] 2-5 parts of long-chain high-carbon fatty alcohol

[0012] 2-5 parts of multifunctional polyether polyol

[0013] Antioxidant 0.2-0.4 parts

[0014] Ultraviolet absorber 0.2-0.4 parts

[0015] Catalyst 0.7-1 part

[0016] Silicone defoamer 0.01-0.03 parts;

[0017] Wherein, the catalyst is one or two of dibutyltin dilaurate and zinc-bismuth composite catalyst;

[0018] The polyurethane prepolymer I component includes the following components in parts by weight:

[0019] Polytetramethylene ether glycol 32.1-62.3 parts

[0020] Aliphatic isocyanate 37.1-67.2 parts

[0021] Antioxidant 0.6-0.8 parts.

[0022] Preferably, the relative molecular mass of the polytetramethylene ether glycol is 1000-3000.

[0023] Preferably, the small molecule polyol is one or two of ethylene glycol, 1,4-butanediol and 1,6-hexanediol.

[0024] Preferably, the multifunctional polyether polyol is one or two of INOVOL C304, INOVOL C305, INOVOL R405 and NJ6209.

[0025] Preferably, the long-chain high-carbon fatty alcohol is one or two of palmityl alcohol, arachidyl alcohol and behenyl alcohol.

[0026] Preferably, the antioxidant is one or both of antioxidant 1076 and antioxidant 1010; the ultraviolet absorber is one or both of UV-1 and UV-531.

[0027] Preferably, the aliphatic isocyanate is one or two of isophorone diisocyanate (IPDI), hexamethylene diisocyanate (HDI), 4,4'-dicyclohexylmethane diisocyanate (HMDI) and methylcyclohexyl diisocyanate (HTDI).

[0028] On the other hand, the present invention provides a method for preparing the above-mentioned yellowing-resistant polyurethane elastomer shoe outsole material, which comprises mixing a composite chain extender P component and a polyurethane prepolymer I component at 60-65° C. evenly, pouring the mixture into a mold at 80-85° C., applying pressure to the gel point, and heating and curing the mixture to obtain the yellowing-resistant polyurethane elastomer shoe outsole material.

[0029] Preferably, the preparation method of the composite chain extender P component comprises the following steps:

[0030] (1) Put polytetramethylene ether glycol, long-chain high-carbon fatty alcohol, and multifunctional polyether polyol into a reaction kettle, evacuate to a vacuum degree of ≤-0.095MPa, heat to 80-85°C, and stir evenly;

[0031] (2) After sampling and testing the water content to be ≤0.05wt.%, add antioxidant and ultraviolet absorber to the reactor, evacuate to a vacuum degree of ≤-0.095MPa, and stir;

[0032] (3) Cooling the materials in the reactor to below 65°C, replenishing nitrogen to normal pressure, adding small molecule polyols, silicone defoaming agents and catalysts, and continuing to stir to obtain a composite chain extender component P.

[0033] Preferably, the preparation method of the polyurethane prepolymer component I comprises the following steps:

[0034] 1) Detect the moisture content of polytetramethylene ether glycol ≤ 0.05wt.%, temperature < 55℃, and set aside;

[0035] 2) Add aliphatic isocyanate into the reactor and stir. After the temperature drops below 40°C, add polytetramethylene ether glycol. After adding all the materials, seal the reactor with nitrogen and maintain a slight positive pressure in the reactor. Stir for 20-30 minutes.

[0036] 3) Raise the temperature to 95-100°C within 1 hour and keep warm for 5-6 hours, during which time add antioxidant and remove bubbles to a vacuum degree of ≤-0.095MPa to obtain polyurethane prepolymer component I.

[0037] Compared with the prior art, the present invention has the following beneficial effects:

[0038] The present invention, when preparing the yellowing-resistant polyurethane elastomer shoe outsole material, can effectively solve the yellowing problem commonly existing in polyurethane shoe outsole materials by adding aliphatic isocyanate without benzene ring structure, and can also improve the disadvantages that the existing benzene ring structure materials are difficult to degrade after use, and are difficult to meet the requirements of green environmental protection materials. At the same time, the present invention can not only solve the problem that the reaction activity of aliphatic products is low and the processability is poor, so that the rapid mold opening demand of shoe outsole products cannot be met by adding long-chain high-carbon fatty alcohols and multifunctional polyether polyols in appropriate amounts, but also greatly improve the mechanical properties of polyether polyurethane elastomers, and meet the demand for low wear of shoe outsole products. The yellowing-resistant polyurethane elastomer shoe outsole material of the present invention adopts a polyether system, so that the shoe outsole product not only has good hydrolysis resistance, meets the lightweight demand, but also has excellent low temperature resistance, and meets the market performance requirements for low temperature resistance, yellowing resistance, high wear resistance and high tear performance CPU shoe outsole. DETAILED DESCRIPTION

[0039] In order to enable persons skilled in the art to better understand the technical solution of the present invention, the technical solution of the present invention will be clearly and completely described below in conjunction with the embodiments of the present invention.

[0040] Unless otherwise specified, the raw materials used in the following examples and comparative examples are conventional commercially available raw materials.

[0041] Some of the raw materials used in the following examples and comparative examples are as follows:

[0042] INOVOL C304, polyether polyol, number average molecular weight 375, Shandong INOVOL New Materials Co., Ltd.;

[0043] INOVOL C305, polyether polyol, number average molecular weight 500, Shandong INOVOL New Materials Co., Ltd.;

[0044] INOVOL R405, polyether polyol, number average molecular weight 448, Shandong INOVOL New Materials Co., Ltd.;

[0045] Palm alcohol, Shandong Fengtong Chemical Co., Ltd.;

[0046] Arachidyl alcohol, Shandong Fengtong Chemical Co., Ltd.;

[0047] Behenyl alcohol, Shandong Fengtong Chemical Co., Ltd.;

[0048] Dibutyltin dilaurate, Nantong Haotai Chemical Products Co., Ltd.;

[0049] Zinc-bismuth composite catalyst, Guangzhou Yourun Synthetic Materials Co., Ltd.;

[0050] SN-6041 silicone defoamer, Shanghai Shenzhu Chemical Technology Co., Ltd.;

[0051] PE-2020, EG / AA polyester polyol, number average molecular weight 2000, Shandong Yinuowei Polyurethane Co., Ltd.;

[0052] Amine DXD-01C catalyst, Shandong Yinuowei Polyurethane Co., Ltd.;

[0053] Polyether polyol DL1000, Shandong Bluestar Dongda Chemical Co., Ltd.;

[0054] n-Octanol, Clariant Chemicals (China) Co., Ltd.

[0055] Example 1

[0056] The yellowing-resistant polyurethane elastomer shoe outsole material of this embodiment comprises a composite chain extender component P and a polyurethane prepolymer component I in a mass ratio of 1:1.34; wherein the preparation method of the composite chain extender component P comprises the following steps:

[0057] (1) 83.89 parts of polytetramethylene ether glycol with a relative molecular mass of 1000, 2 parts of palmityl alcohol, 2 parts of INOVOL C304 and 1 part of INOVOL C305 were placed in a reaction kettle, evacuated to a vacuum degree of ≤-0.095 MPa, heated to 80°C and stirred evenly;

[0058] (2) After sampling and testing the moisture content to be ≤0.05wt.%, add 0.2 parts of antioxidant 1076, 0.1 parts of UV-1, and 0.1 parts of UV-531 into the reactor, evacuate to a vacuum degree of ≤-0.095MPa, and stir for 30 minutes;

[0059] (3) The temperature of the materials in the reactor was lowered to below 65°C, nitrogen was added to normal pressure, 10 parts of ethylene glycol, 0.01 parts of SN-6041 silicone defoamer and 0.7 parts of dibutyltin dilaurate were added, and stirring was continued for 30 minutes to obtain the composite chain extender component P.

[0060] The preparation method of the polyurethane prepolymer I component comprises the following steps:

[0061] 1) Detect the moisture content of polytetramethylene ether glycol ≤ 0.05wt.%, temperature < 55℃, and set aside;

[0062] 2) Add 49.1 parts of IPDI into the reactor and stir. After the temperature drops below 40°C, add 50.1 parts of polytetramethylene ether glycol with a relative molecular mass of 2000. After adding the materials, seal the reactor with nitrogen and maintain a slight positive pressure in the reactor, and stir for 20 minutes;

[0063] 3) The temperature was raised to 95°C within 1 hour and kept at this temperature for 5 hours. During this period, 0.8 parts of antioxidant 1010 were added and the bubbles were removed to a vacuum degree of ≤-0.095 MPa to obtain a polyurethane prepolymer component I having an isocyanate content of 16.3 wt.%.

[0064] The preparation method of the yellowing-resistant polyurethane elastomer shoe outsole material of this embodiment is as follows: after the composite chain extender P component and the polyurethane prepolymer I component are evenly mixed at 60°C, poured into a preheated 80°C mold, pressurized at the gel point, and heated to cure to obtain the yellowing-resistant polyurethane elastomer shoe outsole material.

[0065] Example 2

[0066] The yellowing-resistant polyurethane elastomer shoe outsole material of this embodiment comprises a composite chain extender P component and a polyurethane prepolymer I component in a mass ratio of 1:0.95; wherein the preparation method of the composite chain extender P component comprises the following steps:

[0067] (1) 81.58 parts of polytetramethylene ether glycol with a relative molecular mass of 2000, 4 parts of palmityl alcohol and 2 parts of INOVOL R405 were put into a reaction kettle, evacuated to a vacuum degree of ≤-0.095 MPa, heated to 83°C and stirred evenly;

[0068] (2) After sampling and testing the water content to be ≤0.05wt.%, add 0.1 parts of antioxidant 1010, 0.1 parts of antioxidant 1076, and 0.2 parts of UV-531 into the reactor, evacuate to a vacuum degree of ≤-0.095MPa, and stir for 30 minutes;

[0069] (3) The temperature of the materials in the reactor was lowered to below 65°C, nitrogen was added to normal pressure, 11 parts of 1,4-butanediol, 0.02 parts of SN-6041 silicon defoamer and 1 part of zinc-bismuth composite catalyst were added, and stirring was continued for 30 minutes to obtain a composite chain extender component P.

[0070] The preparation method of the polyurethane prepolymer I component comprises the following steps:

[0071] 1) Detect the moisture content of polytetramethylene ether glycol ≤ 0.05wt.%, temperature < 55℃, and set aside;

[0072] 2) Add 20.2 parts of HMDI and 47 parts of HDI into the reactor and stir. After the temperature drops below 40°C, add 32.1 parts of polytetramethylene ether glycol with a relative molecular mass of 2000. After adding the materials, seal the reactor with nitrogen and maintain a slight positive pressure in the reactor, and stir for 30 minutes;

[0073] 3) The temperature was raised to 98°C within 1 hour and kept at this temperature for 6 hours. During this period, 0.7 parts of antioxidant 1010 were added and the bubbles were removed to a vacuum degree of ≤-0.095 MPa to obtain a polyurethane prepolymer component I having an isocyanate content of 16 wt.%.

[0074] The preparation method of the yellowing-resistant polyurethane elastomer shoe outsole material of this embodiment is as follows: after the composite chain extender P component and the polyurethane prepolymer I component are evenly mixed at 65°C, poured into a preheated 80°C mold, pressurized at the gel point, and heated to cure to obtain the yellowing-resistant polyurethane elastomer shoe outsole material.

[0075] Example 3

[0076] The yellowing-resistant polyurethane elastomer shoe outsole material of this embodiment comprises a composite chain extender component P and a polyurethane prepolymer component I in a mass ratio of 1:1.1; wherein the preparation method of the composite chain extender component P comprises the following steps:

[0077] (1) 77.57 parts of polytetramethylene ether glycol with a relative molecular mass of 1000, 5 parts of behenyl alcohol and 3 parts of NJ6209 were added into a reaction kettle, evacuated to a vacuum degree of ≤-0.095 MPa, heated to 85°C and stirred evenly;

[0078] (2) After sampling and testing the water content to be ≤0.05wt.%, add 0.2 parts of antioxidant 1076 and 0.4 parts of UV-1 into the reactor, evacuate to a vacuum degree of ≤-0.095MPa, and stir for 30 minutes;

[0079] (3) The temperature of the materials in the reactor was lowered to below 65°C, nitrogen was added to normal pressure, 8 parts of 1,4-butanediol, 5 parts of 1,6-hexanediol, 0.03 parts of SN-6041 silicon defoamer and 0.8 parts of zinc-bismuth composite catalyst were added, and stirring was continued for 30 minutes to obtain a composite chain extender component P.

[0080] The preparation method of the polyurethane prepolymer I component comprises the following steps:

[0081] 1) Detect the moisture content of polytetramethylene ether glycol ≤ 0.05wt.%, temperature < 55℃, and set aside;

[0082] 2) Add 40 parts of HTDI into the reactor and stir. After the temperature drops below 40°C, add 59.4 parts of polytetramethylene ether glycol with a relative molecular mass of 3000. After adding the materials, seal the reactor with nitrogen and maintain a slight positive pressure in the reactor, and stir for 30 minutes;

[0083] 3) The temperature was raised to 100°C within 1 hour and kept at this temperature for 5 hours. During this period, 0.6 parts of antioxidant 1010 were added and the bubbles were removed to a vacuum degree of ≤-0.095 MPa to obtain a polyurethane prepolymer component I having an isocyanate content of 16.8 wt.%.

[0084] The preparation method of the yellowing-resistant polyurethane elastomer shoe outsole material of this embodiment is as follows: after the composite chain extender P component and the polyurethane prepolymer I component are evenly mixed at 60°C, poured into a preheated 85°C mold, pressurized at the gel point, and heated to cure to obtain the yellowing-resistant polyurethane elastomer shoe outsole material.

[0085] Example 4

[0086] The yellowing-resistant polyurethane elastomer shoe outsole material of this embodiment comprises a composite chain extender P component and a polyurethane prepolymer I component in a mass ratio of 1:0.98; wherein the preparation method of the composite chain extender P component comprises the following steps:

[0087] (1) 77.39 parts of polytetramethylene ether glycol with a relative molecular mass of 2000, 4 parts of arachidyl alcohol and 5 parts of INOVOL C305 were placed in a reaction kettle, evacuated to a vacuum degree of ≤-0.095 MPa, heated to 80°C and stirred evenly;

[0088] (2) After sampling and testing the water content to be ≤0.05wt.%, add 0.4 parts of antioxidant 1010 and 0.4 parts of UV-1 into the reactor, evacuate to a vacuum degree of ≤-0.095MPa, and stir for 30 minutes;

[0089] (3) The temperature of the materials in the reactor was lowered to below 65°C, nitrogen was added to normal pressure, 12 parts of 1,4-butanediol, 0.01 parts of SN-6041 silicon defoamer, 0.6 parts of dibutyltin dilaurate and 0.2 parts of zinc-bismuth composite catalyst were added, and stirring was continued for 25 minutes to obtain a composite chain extender component P.

[0090] The preparation method of the polyurethane prepolymer I component comprises the following steps:

[0091] 1) Detect the moisture content of polytetramethylene ether glycol ≤ 0.05wt.%, temperature < 55℃, and set aside;

[0092] 2) Add 37.1 parts of HDI into the reactor and stir. After the temperature drops below 40°C, add 18.7 parts of polytetramethylene ether glycol with a relative molecular mass of 2000 and 43.6 parts of polytetramethylene ether glycol with a relative molecular mass of 3000. After adding the materials, seal the reactor with nitrogen and maintain a slight positive pressure in the reactor, and stir for 20 minutes;

[0093] 3) The temperature was raised to 95°C within 1 hour and kept at this temperature for 6 hours. During this period, 0.6 parts of antioxidant 1010 were added and the bubbles were removed to a vacuum degree of ≤-0.095 MPa to obtain a polyurethane prepolymer component I having an isocyanate content of 16.3 wt.%.

[0094] The preparation method of the yellowing-resistant polyurethane elastomer shoe outsole material of this embodiment is as follows: after the composite chain extender P component and the polyurethane prepolymer I component are evenly mixed at 64°C, poured into a preheated 82°C mold, pressurized at the gel point, and heated to cure to obtain the yellowing-resistant polyurethane elastomer shoe outsole material.

[0095] Example 5

[0096] The yellowing-resistant polyurethane elastomer shoe outsole material of this embodiment comprises a composite chain extender P component and a polyurethane prepolymer I component in a mass ratio of 1:0.96; wherein the preparation method of the composite chain extender P component comprises the following steps:

[0097] (1) 80.59 parts of polytetramethylene ether glycol with a relative molecular mass of 2000, 2 parts of behenyl alcohol, 3 parts of palmityl alcohol and 2 parts of NJ6209 were put into a reaction kettle, evacuated to a vacuum degree of ≤-0.095 MPa, heated to 80°C and stirred evenly;

[0098] (2) After sampling and testing the moisture content to be ≤0.05wt.%, add 0.3 parts of antioxidant 1076 and 0.3 parts of UV-531 into the reactor, evacuate to a vacuum degree of ≤-0.095MPa, and stir for 25 minutes;

[0099] (3) The temperature of the materials in the reactor was lowered to below 65°C, nitrogen was added to normal pressure, 11 parts of 1,4-butanediol, 0.01 parts of SN-6041 silicon defoamer and 0.8 parts of zinc-bismuth composite catalyst were added, and stirring was continued for 30 minutes to obtain a composite chain extender component P.

[0100] The preparation method of the polyurethane prepolymer I component comprises the following steps:

[0101] 1) Detect the moisture content of polytetramethylene ether glycol ≤ 0.05wt.%, temperature < 55℃, and set aside;

[0102] 2) Add 53.3 parts of HMDI into the reactor and stir. After the temperature drops below 40°C, add 46.1 parts of polytetramethylene ether glycol with a relative molecular mass of 3000. After adding the materials, seal the reactor with nitrogen and maintain a slight positive pressure in the reactor, and stir for 25 minutes;

[0103] 3) The temperature was raised to 95°C within 1 hour and kept at this temperature for 5.5 hours. During this period, 0.3 parts of antioxidant 1010 and 0.3 parts of antioxidant 1076 were added, and the bubbles were removed until the vacuum degree was ≤-0.095 MPa to obtain a polyurethane prepolymer component I with an isocyanate content of 15.5 wt.%.

[0104] The preparation method of the yellowing-resistant polyurethane elastomer shoe outsole material of this embodiment is as follows: after the composite chain extender P component and the polyurethane prepolymer I component are evenly mixed at 60°C, poured into a preheated 80°C mold, pressurized at the gel point, and heated to cure to obtain the yellowing-resistant polyurethane elastomer shoe outsole material.

[0105] Comparative Example 1

[0106] The difference from Example 2 is that polyester polyol PE-2020 is used to replace the polytetramethylene ether glycol in Example 2.

[0107] Comparative Example 2

[0108] The difference from Example 1 is that palmityl alcohol is not added to the composite chain extender component P, and the added amount of polytetramethylene ether glycol is 85.89 parts.

[0109] Comparative Example 3

[0110] The difference from Example 1 is that in the composite chain extender component P, the amount of palmityl alcohol added is 6 parts, and the amount of polytetramethylene ether glycol added is 79.89 parts.

[0111] The preparation method of the polyurethane elastomer shoe outsole material of Comparative Example 3 is as follows: after the composite chain extender P component and the polyurethane prepolymer I component are evenly mixed at 60°C, poured into a preheated 80°C mold, pressurized at the gel point, heated and cured, and the mold opening strength is poor for 20 minutes to obtain the polyurethane elastomer shoe outsole material.

[0112] Comparative Example 4

[0113] The difference from Example 2 is that INOVOL R405 is not added to the composite chain extender component P, and the added amount of polytetramethylene ether glycol is 83.59 parts.

[0114] The preparation method of the polyurethane elastomer shoe outsole material of Comparative Example 4 is as follows: after the composite chain extender P component and the polyurethane prepolymer I component are evenly mixed at 65°C, they are poured into a preheated 80°C mold, pressurized at the gel point, heated and cured, and the mold opening strength is poor after 30 minutes, and the mold cannot be formed, and the processability is poor.

[0115] Comparative Example 5

[0116] The difference from Example 3 is that in the composite chain extender component P, the zinc-bismuth composite catalyst in Example 3 is replaced by an amine DXD-01C catalyst.

[0117] The preparation method of the polyurethane elastomer shoe outsole material of Comparative Example 5 is as follows: after the composite chain extender P component and the polyurethane prepolymer I component are evenly mixed at 60° C., they are poured into a preheated 85° C. mold, which has poor toughness and poor processability.

[0118] Comparative Example 6

[0119] The difference from Example 4 is that in the polyurethane prepolymer I component, 26 parts of aromatic isocyanate MDI-100 and 11.1 parts of aromatic isocyanate carbodiimide-modified MDI are used to replace the HDI in Example 4.

[0120] Comparative Example 7

[0121] The difference from Example 1 is that polyether polyol DL1000 is used to replace the polytetramethylene ether glycol with a relative molecular mass of 1000 in Example 1.

[0122] Comparative Example 8

[0123] The difference from Example 1 is that n-butanol is used to replace the palmityl alcohol in Example 1.

[0124] The performance tests were conducted on the polyurethane elastomer outsole materials prepared in Examples 1-5 and Comparative Examples 1-8. The test results are shown in Table 1-2. Among them, the hardness is tested with reference to GB / T 531.1-2008 Vulcanized rubber or thermoplastic rubber indentation hardness test method Part 1: Shore hardness method (Shore hardness)"; the tensile strength is tested with reference to GB / T 528-2009 Determination of tensile stress-strain properties of vulcanized rubber or thermoplastic rubber; the elongation at break is tested with reference to GB / T 528-2009 Determination of tensile stress-strain properties of vulcanized rubber or thermoplastic rubber; the tear strength is tested with reference to GB / T 529-2008 Determination of tear strength of vulcanized rubber or thermoplastic rubber (trouser-shaped, right-angled and crescent-shaped specimens); the DIN abrasion is tested with reference to GB / T 9867-2008 Determination of wear resistance of vulcanized rubber or thermoplastic rubber (rotating roller abrasion machine method); the UV yellowing resistance is tested with reference to GB / T 29778-2013 The low-temperature hardness is tested by placing the sample in the -20℃ freezer of the refrigerator for 24 hours and then taking it out, and immediately testing it with reference to GB / T 531.1-2008 Test method for indentation hardness of vulcanized rubber or thermoplastic rubber Part 1: Shore hardness method (Shore hardness)". The hydrolysis resistance is tested by placing a sample of 150mm long, 150mm wide and 2mm thick in a constant temperature and humidity chamber, setting the temperature to 70℃ and the humidity to 95%RH, taking it out after 120 hours, comparing the color change of the sample before and after hydrolysis, and rating it with the GB250 color change card. The aging performance is tested with reference to ASTM D573 Standard Test Method for Rubber-Aging in Air Oven. The density is tested with reference to GB-T 4472-2011 Determination of Density and Relative Density of Chemical Products.

[0125] Table 1 Performance test results of the yellowing-resistant polyurethane elastomer shoe outsole materials of Examples 1-5

[0126]

[0127] Table 2 Performance test results of polyurethane elastomer outsole materials of comparative examples 1-8

[0128]

[0129] From the performance test results of Comparative Example 1 and Example 2 in Table 1-2, it can be seen that the polyester polyurethane elastomer prepared in Comparative Example 1 has excellent mechanical properties due to the presence of ester groups with strong polarity, but its hydrolysis resistance is poor and its density is high. The polyether polyurethane elastomer prepared in Example 2 has a low density, which meets the demand for lightweight shoe outsole products. Although the polarity of the soft segment of the polyether polyurethane elastomer is weaker and its mechanical strength is not as good as that of the polyester polyurethane elastomer, it does not contain an ester group that is easily hydrolyzed, and its hydrolysis resistance is worse than that of the polyester polyurethane elastomer, and the ether group contained is easy to rotate, so it has good flexibility and low temperature resistance.

[0130] Comparative Example 1 and Comparative Example 2 show that the structural feature of long-chain high-carbon aliphatic alcohol is that one end has a long hydrocarbon chain, and the other end is connected to a hydrophilic hydroxyl functional group. This structure enables the molecules to be oriented on the liquid surface or interface, thereby reducing the surface energy and enhancing the wear resistance of the product. In addition, the present invention disrupts the regularity of the main chain structure of polytetramethylene ether glycol by introducing a long-chain high-carbon aliphatic alcohol side chain, weakens the soft segment crystallization ability, and further improves the low temperature resistance on the basis of the polyether polyurethane elastomer. A small amount of long-chain high-carbon aliphatic alcohol is added to the system as a microphase separation promoter, so that the soft segment region establishes a macromolecular equilibrium conformation when the system solidifies, and the hard segment region is close to the equilibrium crystallinity allowed by its regularity, that is, the system reaches an equilibrium state, thereby improving the microphase separation degree of the soft and hard segments. At the same time, the long-chain high-carbon aliphatic alcohol of the present invention is a long-chain segment unit alcohol, so that the molecular chain functionality is significantly reduced, and then the elongation at break and the tear strength of the shoe outsole product are significantly improved. At the same time, the reduction in system functionality is not friendly to the demand for rapid mold opening of shoe outsole products, and the molding is poor. As shown in Comparative Example 3, when long-chain high-carbon fatty alcohols are added in excess, the tear strength of the polyurethane elastomer shoe outsole material is significantly improved, but the operation processability is poor. The addition of multifunctional polyether polyols can effectively promote the crosslinking of the system, thereby improving the problem of poor processability. However, it can be seen from Example 2 and Comparative Example 4 that the addition of multifunctional polyether polyols will cause a decrease in tear strength and elongation at break, so the addition amount of the two components is crucial to meet both tear performance and process performance.

[0131] It can be seen from Example 3 and Comparative Example 5 that when the system uses an amine DXD-01C catalyst, the early gel and the growth rate of toughness in the later stage of the system are slow, and the mechanical properties of the prepared polyurethane elastomer shoe outsole material are poor. It can be seen from Example 4 and Comparative Example 6 that the polyurethane elastomer shoe outsole material prepared using aliphatic isocyanates without benzene rings has better yellowing resistance than the polyurethane elastomer shoe outsole material prepared using aromatic isocyanates, and its aging performance is also better. It can be seen from Example 1 and Comparative Example 7 that polyether polyol DL1000 contains side methyl groups, which leads to a weakening of the molecular force, and the molecular structure is not as regular as that of polytetramethylene ethers, so the strength of the prepared polyurethane elastomer shoe outsole material is poorer than that of the polyurethane elastomer shoe outsole material prepared using polytetramethylene ethers. It can be seen from Example 1 and Comparative Example 8 that replacing the long-chain high-carbon fatty alcohol with n-octanol with a relatively short molecular chain results in the main chain structure of polytetramethylene ether glycol still having a relatively strong regularity, the soft segment crystallization ability is relatively less weakened, and the system functionality is still relatively high. Therefore, the prepared polyurethane elastomer shoe outsole material has poor low temperature resistance and trouser-shaped tear strength.

Claims

1. Yellowing-resistant polyurethane elastomer shoe outsole material, characterized in that: It includes a composite chain extender P component and a polyurethane prepolymer I component in a mass ratio of 1:(0.95-1.34); Wherein, the composite chain extender P component includes the following components in parts by weight: Polytetramethylene ether glycol 77.39-83.89 parts 10-13 parts of small molecule polyol 2-5 parts of long-chain high-carbon fatty alcohol 2-5 parts of multifunctional polyether polyol Antioxidant 0.2-0.4 parts Ultraviolet absorber 0.2-0.4 parts Catalyst 0.7-1 part Silicone defoamer 0.01-0.03 parts; Wherein, the catalyst is one or two of dibutyltin dilaurate and zinc-bismuth composite catalyst; The polyurethane prepolymer I component includes the following components in parts by weight: Polytetramethylene ether glycol 32.1-62.3 parts Aliphatic isocyanate 37.1-67.2 parts Antioxidant 0.6-0.8 parts; The multifunctional polyether polyol is one or two of INOVOL C304, INOVOL C305, INOVOL R405 and NJ6209; the long-chain high-carbon fatty alcohol is one or two of palmityl alcohol, arachidyl alcohol and behenyl alcohol.

2. The yellowing-resistant polyurethane elastomer shoe outsole material according to claim 1, characterized in that: The relative molecular mass of the polytetramethylene ether glycol is 1000-3000.

3. The yellowing-resistant polyurethane elastomer shoe outsole material according to claim 1, characterized in that: The small molecule polyol is one or two of ethylene glycol, 1,4-butanediol and 1,6-hexanediol.

4. The yellowing-resistant polyurethane elastomer shoe outsole material according to claim 1, characterized in that: The antioxidant is one or both of antioxidant 1076 and antioxidant 1010; the ultraviolet absorber is one or both of UV-1 and UV-531.

5. The yellowing-resistant polyurethane elastomer shoe outsole material according to claim 1, characterized in that: The aliphatic isocyanate is one or two of isophorone diisocyanate, hexamethylene diisocyanate, 4,4'-dicyclohexylmethane diisocyanate and methylcyclohexyl diisocyanate.

6. The method for preparing the yellowing-resistant polyurethane elastomer shoe outsole material according to any one of claims 1 to 5, characterized in that: The composite chain extender P component and the polyurethane prepolymer I component are uniformly mixed at 60-65°C, poured into a mold at 80-85°C, pressurized at the gel point, and heated to cure to obtain a yellowing-resistant polyurethane elastomer shoe outsole material.

7. The method for preparing the yellowing-resistant polyurethane elastomer shoe outsole material according to claim 6, characterized in that: The preparation method of the composite chain extender P component comprises the following steps: (1) Put polytetramethylene ether glycol, long-chain high-carbon fatty alcohol, and multifunctional polyether polyol into a reaction kettle, evacuate to a vacuum degree of ≤-0.095MPa, heat to 80-85°C, and stir evenly; (2) After sampling and testing the water content to be ≤0.05wt.%, add antioxidant and ultraviolet absorber to the reactor, evacuate to a vacuum degree of ≤-0.095MPa, and stir; (3) Cooling the materials in the reactor to below 65°C, replenishing nitrogen to normal pressure, adding small molecule polyols, silicone defoaming agents and catalysts, and continuing to stir to obtain a composite chain extender component P.

8. The method for preparing the yellowing-resistant polyurethane elastomer shoe outsole material according to claim 6, characterized in that: The preparation method of the polyurethane prepolymer component I comprises the following steps: 1) Detect the moisture content of polytetramethylene ether glycol ≤ 0.05wt.%, temperature < 55℃, and set aside; 2) Add aliphatic isocyanate into the reactor and stir. After the temperature drops below 40°C, add polytetramethylene ether glycol. After adding all the materials, seal the reactor with nitrogen and maintain a slight positive pressure in the reactor. Stir for 20-30 minutes. 3) Raise the temperature to 95-100°C within 1 hour and keep warm for 5-6 hours, during which time add antioxidant and remove bubbles to a vacuum degree of ≤-0.095MPa to obtain polyurethane prepolymer component I.

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