A modified nylon elastomer, an elastic composite material, its preparation method and application, and an elastic shoe sole.

Abstract

This invention provides a modified nylon elastomer, an elastic composite material, its preparation method and application, and an elastic shoe sole, relating to the field of footwear manufacturing technology. The modified nylon elastomer of this invention, by weight, comprises the following raw materials: 20-30 parts nylon elastomer, 50-60 parts polyolefin block copolymer, 10-20 parts ethylene-methacrylic acid copolymer resin, and 0.5-0.8 parts stearic acid. This invention modifies the nylon elastomer by blending it with the polyolefin block copolymer. The polyolefin block copolymer has a unique alternating soft and hard block structure, giving the modified nylon elastomer high rigidity and high resilience, and effectively controlling the dimensional changes of the modified nylon elastomer foamed products. Simultaneously, the ethylene-methacrylic acid copolymer resin can improve the dispersibility and compatibility of the nylon elastomer and the polyolefin block copolymer.

Description

Technical Field

[0001] This invention belongs to the field of footwear manufacturing technology, specifically relating to a modified nylon elastomer, an elastic composite material, its preparation method and application, and an elastic shoe sole. Background Technology

[0002] With the rapid development of the athletic shoe market, consumers have increasingly higher demands for athletic shoes, requiring not only fashionable appearance but also comfortable wear. At the same time, the performance requirements for sole materials are also rising, with softness, comfort, and lightweight design being the main development trends.

[0003] Most existing athletic shoe soles are made of wear-resistant ethylene vinyl acetate copolymer (EVA) foam material. However, the soles made of this material have technical defects such as high density and poor rebound performance. Moreover, after wearing them for a period of time, they will collapse and feel uncomfortable, which seriously affects the comfort of consumers wearing athletic shoes. Summary of the Invention

[0004] The purpose of this invention is to provide a modified nylon elastomer, an elastic composite material, a preparation method and application thereof, and an elastic shoe sole. The elastic shoe sole prepared using the elastic composite material containing the nylon elastomer described in this invention has the advantages of low density and high resilience.

[0005] To achieve the objectives of this invention, the following technical solutions are provided:

[0006] A modified nylon elastomer, prepared by weight, comprises: 20-30 parts of nylon elastomer, 50-60 parts of polyolefin block copolymer, 10-20 parts of ethylene-methacrylic acid copolymer resin, and 0.5-0.8 parts of stearic acid.

[0007] This invention provides a method for preparing the modified nylon elastomer described above, comprising the following steps:

[0008] The modified nylon elastomer is obtained by compounding nylon elastomer, polyolefin block copolymer, ethylene-methacrylic acid copolymer resin and stearic acid.

[0009] Preferably, the mixing temperature is 180–200°C and the time is 1000–1200 seconds.

[0010] Preferably, the mixing is carried out in a twin-screw extruder, wherein the main rotor speed of the twin-screw extruder is 550-600 r / min.

[0011] The present invention also provides an elastic composite material, wherein the raw materials, by weight, include: 55-65 parts of modified nylon elastomer, 30-40 parts of ethylene vinyl acetate resin copolymer, 0.5-1 parts of di-tert-butyl peroxide, 0.5-0.8 parts of stearic acid, 0.5-1 parts of zinc oxide, and 3-4 parts of foaming agent; wherein the modified nylon elastomer is the modified nylon elastomer described in the above technical solution or the modified nylon elastomer prepared by the preparation method described in the above technical solution.

[0012] This invention also provides a method for preparing an elastic composite material, comprising the following steps:

[0013] The modified nylon elastomer, ethylene vinyl acetate copolymer, stearic acid and zinc oxide were first compounded to obtain the first compound system.

[0014] The first mixing system, di-tert-butyl peroxide, and foaming agent are mixed a second time to obtain the elastic composite material.

[0015] Preferably, the temperature of the first mixing is 95-100°C and the time is 600-700s; the temperature of the second mixing is 110-115°C and the time is 700-750s.

[0016] This invention provides the application of the elastic composite material described in the above technical solution or the elastic composite material prepared by the preparation method described in the above technical solution in shoe soles.

[0017] The present invention also provides an elastic shoe sole, which is obtained by sequentially foaming, shaping and molding the elastic composite material described in the above technical solution or the elastic composite material prepared by the preparation method described in the above technical solution.

[0018] Preferably, the foaming temperature is 175–180°C and the time is 500–550 seconds.

[0019] This invention provides a modified nylon elastomer, comprising, by weight, 20-30 parts of nylon elastomer, 50-60 parts of polyolefin block copolymer, 10-20 parts of ethylene-methacrylic acid copolymer resin, and 0.5-0.8 parts of stearic acid. This invention modifies the nylon elastomer by blending it with the polyolefin block copolymer. The polyolefin block copolymer possesses a unique alternating soft and hard block structure, giving the modified nylon elastomer high rigidity and high resilience, and effectively controlling the dimensional changes of the modified nylon elastomer foamed products. Simultaneously, the ethylene-methacrylic acid copolymer resin improves the dispersibility and compatibility of the nylon elastomer and the polyolefin block copolymer.

[0020] As shown in the results of the embodiments of the present invention, the elastic shoe sole prepared from the elastic composite material containing the modified nylon elastomer described in the present invention has a resilience of 68% and a density of 0.13 g / cm³. 3 It has the advantages of low density and high resilience. Detailed Implementation

[0021] This invention provides a modified nylon elastomer, which, by mass, comprises: 20-30 parts of nylon elastomer, 50-60 parts of polyolefin block copolymer, 10-20 parts of ethylene-methacrylic acid copolymer resin, and 0.5-0.8 parts of stearic acid.

[0022] In this invention, unless otherwise specified, all raw materials used in the preparation are preferably commercially available products well known to those skilled in the art.

[0023] In this invention, the raw materials for preparing the modified nylon elastomer include 20-30 parts, preferably 25 parts, of nylon elastomer by weight. In this invention, the melting point of the nylon elastomer (PEBA) is preferably 200-240°C. The nylon elastomer used in this invention is preferably PA12, sourced from Evonik Industries AG, Germany.

[0024] In this invention, the raw materials for preparing the modified nylon elastomer, by weight, include 50-60 parts, preferably 55 parts, of a polyolefin block copolymer. In this invention, the polyolefin block copolymer is preferably OBC9530, derived from Dow Chemical. In this invention, the polyolefin block copolymer is a rare hydrocarbon copolymer with a unique alternating soft and hard block structure, which enables the modified nylon elastomer to possess high rigidity and high resilience.

[0025] In this invention, the raw materials for preparing the modified nylon elastomer include 10-20 parts, preferably 15 parts, of ethylene-methacrylic acid copolymer resin by weight. In this invention, the ethylene-methacrylic acid copolymer resin (EMAA) is preferably ET530H, sourced from JPC Corporation of Japan. In this invention, the ethylene-methacrylic acid copolymer resin acts as a compatibilizer, improving the dispersibility and compatibility of the nylon elastomer and the polyolefin block copolymer.

[0026] In this invention, the raw materials for preparing the modified nylon elastomer include 0.5 to 0.8 parts, preferably 0.6 parts, of stearic acid by weight. In this invention, the stearic acid is preferably sourced from Zhejiang Liuhe Company. In this invention, stearic acid serves to lubricate machinery and prevent charring during processing.

[0027] In this invention, the melting point of the modified nylon elastomer is preferably <120°C, more preferably 110-115°C.

[0028] This invention provides a method for preparing the modified nylon elastomer described above, comprising the following steps:

[0029] The modified nylon elastomer is obtained by compounding nylon elastomer, polyolefin block copolymer, ethylene-methacrylic acid copolymer resin and stearic acid.

[0030] In this invention, the mixing temperature is preferably 180-200°C; the mixing time is preferably 1000-1200s.

[0031] In this invention, the mixing is preferably carried out in a twin-screw extruder; the main engine speed of the twin-screw extruder is preferably 500-600 r / min. In this invention, the twin-screw extruder is preferably a Coperyl STS-65 twin-screw extruder.

[0032] In this invention, after mixing in a twin-screw extruder, the product is further granulated. The granulation is preferably performed in a granulator, and preferably a Jucheng granulator. This invention does not impose any special limitations on the granulation conditions; conventional granulation conditions in the art can be used.

[0033] The present invention also provides an elastic composite material, wherein the raw materials, by weight, include: 55-65 parts of modified nylon elastomer, 30-40 parts of ethylene vinyl acetate resin copolymer, 0.5-1 parts of di-tert-butyl peroxide, 0.5-0.8 parts of stearic acid, 0.5-1 parts of zinc oxide, and 3-4 parts of foaming agent; wherein the modified nylon elastomer is the modified nylon elastomer described in the above technical solution or the modified nylon elastomer prepared by the preparation method described in the above technical solution.

[0034] In this invention, the raw materials for preparing the elastic composite material include 55 to 65 parts, preferably 60 parts, of modified nylon elastomer, by mass.

[0035] In this invention, the raw materials for preparing the elastic composite material include 30-40 parts, preferably 35 parts, of vinyl acetate copolymer by weight. In this invention, the vinyl acetate content in the vinyl acetate copolymer (EVA) is preferably 15-28%, more preferably 26%. In this invention, the vinyl acetate copolymer is preferably sourced from the Formosa Plastics Group. The EVA of this invention, due to the introduction of vinyl acetate monomers into the molecular chain, improves the flexibility, impact resistance, filler compatibility, and heat-sealing performance of the elastic composite material.

[0036] In this invention, the raw materials for preparing the elastic composite material include 0.5 to 1 part, preferably 0.6 to 0.8 parts, of di-tert-butyl peroxide (BIBP) by weight. In this invention, the di-tert-butyl peroxide (BIBP) is preferably 14S-FL, sourced from Norion Chemicals (Ningbo) Co., Ltd.

[0037] In this invention, the raw materials for preparing the elastic composite material include 0.5 to 0.8 parts, preferably 0.6 parts, of stearic acid by weight. Preferably, the stearic acid used in this invention is the same as described above.

[0038] In this invention, the raw materials for preparing the elastic composite material include 0.5 to 1 part zinc oxide, preferably 0.8 parts, by weight. The zinc oxide used in this invention is preferably Baishi brand zinc oxide, sourced from Shanghai Jinghua Chemical Plant Co., Ltd. In this invention, zinc oxide has the function of shortening the foaming time.

[0039] In this invention, the raw materials for preparing the elastic composite material include 3-4 parts, preferably 3.5 parts, of a foaming agent by weight. In this invention, the foaming agent is preferably a low-temperature series foaming agent, and the foaming value of the low-temperature series foaming agent is preferably 150-200 mL / g. In a specific embodiment of this invention, AC3000 foaming agent, sourced from Fujian Jinlang Fine Chemical Co., Ltd., is specifically used.

[0040] This invention also provides a method for preparing an elastic composite material, comprising the following steps:

[0041] The modified nylon elastomer, ethylene vinyl acetate copolymer, stearic acid and zinc oxide were first compounded to obtain the first compound system.

[0042] The first mixing system, di-tert-butyl peroxide, and foaming agent are mixed a second time to obtain the elastic composite material.

[0043] This invention involves a first compounding of modified nylon elastomer, ethylene vinyl acetate copolymer, stearic acid, and zinc oxide to obtain a first compounding system. In this invention, the preferred temperature for the first compounding is 95–100°C, and the preferred time is 600–700 seconds.

[0044] After obtaining the first mixing system, the present invention further involves a second mixing of the first mixing system, di-tert-butyl peroxide, and a foaming agent to obtain an elastic composite material. In this invention, the preferred temperature for the second mixing is 110–115°C, and the preferred time is 700–750 seconds.

[0045] The present invention does not have any special limitations on the equipment for the first and second mixing processes; any mixing equipment known to those skilled in the art can be used.

[0046] This invention provides the application of the elastic composite material described in the above technical solution or the elastic composite material prepared by the preparation method described in the above technical solution in shoe soles.

[0047] The present invention also provides an elastic shoe sole, which is obtained by sequentially foaming, shaping and molding the elastic composite material described in the above technical solution or the elastic composite material prepared by the preparation method described in the above technical solution.

[0048] In this invention, the foaming temperature is preferably 175-180°C, and the foaming time is preferably 500-550 seconds.

[0049] In this invention, the preferred conditions for the shaping process are: sequentially maintaining a constant temperature of 90–95°C for 5–10 min, 80–85°C for 5–10 min, 70–75°C for 5–10 min, and 60–65°C for 5–10 min. In this invention, the shaping process is preferably carried out in a constant temperature chamber, and the rotation speed of the chamber is preferably 2.5–3 r / min, more preferably 2.6–2.7 r / min.

[0050] The present invention also preferably includes allowing the shaped material to stand. In the present invention, the standing temperature is preferably room temperature; the standing time is preferably 24 hours.

[0051] In this invention, the molding temperature is preferably 170-175°C; the pressure is preferably 80-100 MPa; and the heating time is preferably 200-250 s.

[0052] This invention also includes cooling the molded product. Preferably, circulating water is used for cooling, and the cooling time is preferably 200–250 seconds.

[0053] In this invention, the elasticity of the elastic sole is preferably 65-70%, more preferably 68%.

[0054] In this invention, the density of the elastic sole is preferably 0.12–0.15 g / cm³. 3 More preferably, it is 0.13 g / cm³. 3 .

[0055] In this invention, the compressibility of the elastic sole is preferably 30-40%, more preferably 38%.

[0056] To further illustrate the present invention, the modified nylon elastomer and elastic composite material provided by the present invention will be described in detail below with reference to the embodiments, but they should not be construed as limiting the scope of protection of the present invention.

[0057] The sources and parameters of the raw materials used in the preparation of the present invention in the following embodiments, application examples and comparative examples are as follows:

[0058] Nylon elastomer: PA12, sourced from Evonik Industries AG, Germany;

[0059] Polyolefin block copolymer: OBC9530, sourced from Dow Chemical;

[0060] Ethylene-methacrylic acid copolymer resin: ET530H, sourced from JPC Corporation, Japan;

[0061] Stearic acid: sourced from Zhejiang Liuhe Company;

[0062] Ethylene vinyl acetate copolymer: The vinyl acetate content is 26%, sourced from Formosa Plastics Group;

[0063] Di-tert-butyl peroxide: 14S-FL, sourced from Norion Chemicals (Ningbo) Co., Ltd.;

[0064] Zinc oxide: Baishi brand zinc oxide, sourced from Shanghai Jinghua Chemical Plant Co., Ltd.;

[0065] Foaming agent: AC3000, foaming value 200mL / g, Fujian Jinlang Fine Chemical Co., Ltd.

[0066] Example 1

[0067] Weigh 20 kg of nylon elastomer, 60 kg of polyolefin block copolymer, 20 kg of ethylene-methacrylic acid copolymer resin and 0.5 kg of stearic acid and place them in a twin-screw extruder. Mix them at 180℃ and 600 r / min for 1200 s to obtain modified nylon elastomer.

[0068] Example 2

[0069] Weigh 65 kg of the modified nylon elastomer described in Example 1, 30 kg of ethylene vinyl acetate copolymer, 0.5 kg of stearic acid and 1 kg of zinc oxide and mix them at 95°C for 600 s to obtain the first mixing system;

[0070] The first mixing system, 0.5 kg of di-tert-butyl peroxide and 3 kg of foaming agent were mixed at 115°C for 750 s to obtain an elastic composite material.

[0071] Application Example 1

[0072] The elastic composite material described in Example 2 was placed in a foaming mold and foamed at 175°C for 550 seconds. Then, it was placed in a molding mold and placed in a constant temperature chamber. The mixture was then kept at 90°C for 10 minutes, 80°C for 10 minutes, 70°C for 10 minutes, and 60°C for 10 minutes at a speed of 3 r / min for shaping. After being removed, the mixture was left to stand for 24 hours. After cooling, the surface was cleaned. The mixture was then placed back into the molding mold and molded at 175°C and 100 MPa for 250 seconds. After cooling with circulating water for 200 seconds, the elastic shoe sole was obtained.

[0073] Comparative Example 1

[0074] Weigh 30 kg of ethylene vinyl acetate resin copolymer, 0.5 kg of stearic acid and 1 kg of zinc oxide and mix them at 95°C for 600 s to obtain the first mixing system; mix the first mixing system, 0.5 kg of di-tert-butyl peroxide and 3 kg of foaming agent at 115°C for 750 s to obtain the elastic composite material.

[0075] The elastic composite material was placed in a foaming mold and foamed at 175°C for 550 seconds. Then, it was placed in a molding mold and placed in a constant temperature chamber. The mold was then heated sequentially at 90°C for 10 minutes, 80°C for 10 minutes, 70°C for 10 minutes, and 60°C for 10 minutes to set the shape. After removal, the mold was left to stand for 24 hours. After cooling, the surface was cleaned. The mold was then placed in the molding mold again and molded at 175°C and 100MPa for 250 seconds. After cooling with circulating water for 200 seconds, the elastic shoe sole (EVA shoe sole) was obtained.

[0076] Test case

[0077] The performance of the elastic sole described in Case 1 and Comparative Example 1 was tested, and the specific test methods are as follows:

[0078] Hardness testing was conducted according to GB / T3903.4 standard;

[0079] The resilience test was conducted according to GB / T1681.91 standard;

[0080] The compressibility test was conducted in accordance with the GB / T10653 standard;

[0081] Density testing was conducted in accordance with GB / T533.

[0082] The abrasion test was conducted according to the GB / T3903 standard;

[0083] The specific method for the flexibility test is as follows: the above-mentioned shoe sole is bent back and forth 80,000 times under the condition of 23℃ (±3℃), and it is observed whether it breaks;

[0084] The specific method for the low-temperature embrittlement performance test is as follows: the above-mentioned shoe sole is bent and folded back 40,000 times at -20℃, and then it is taken out and observed whether it breaks.

[0085] The specific method for high-temperature resilience testing is as follows: place the above-mentioned shoe sole in an oven and keep it at 50℃ for 2 hours. After taking it out, test the high-temperature resilience according to GB / T1681.91 standard.

[0086] The test results are shown in Table 1.

[0087] Table 1 shows the test results of the elastic sole performance described in Application Example 1 and Comparative Example 1.

[0088] Source of shoe soles Application Example 1 Comparative Example 1 Hardness (c) 45 45 Resilience (%) 68 45 Compressibility (%) 38 42 <![CDATA[Density (g / cm 3 )]]> 0.13 0.22 Abrasion marks (mm) 12 14 Low temperature embrittlement Unbreakable Fine cracks High-temperature resilience (%) 70 48 flexibility Unbreakable Unbreakable

[0089] As shown in Table 1, the elastic soles made from the elastic composite material containing the modified nylon elastomer described in this invention exhibit superior density, resilience, and abrasion resistance (wear marks) compared to conventional EVA soles. They possess the advantages of low density and high resilience, significantly improving the wearer's comfort. Furthermore, the elastic soles prepared in this invention have a resilience of 68%, demonstrating excellent impact resistance.

[0090] Although the above embodiments have provided a detailed description of the present invention, they are only some embodiments of the present invention, and not all embodiments. People can obtain other embodiments based on these embodiments without creative effort, and these embodiments all fall within the protection scope of the present invention.

Claims

1. An elastic composite material, wherein the raw materials prepared by weight are: 55-65 parts of modified nylon elastomer, 30-40 parts of ethylene vinyl acetate resin copolymer, 0.5-1 parts of di-tert-butyl peroxide, 0.5-0.8 parts of stearic acid, 0.5-1 parts of zinc oxide, and 3-4 parts of foaming agent; The modified nylon elastomer is prepared by the following raw materials in parts by mass: 20-30 parts of nylon elastomer, 50-60 parts of polyolefin block copolymer, 10-20 parts of ethylene-methacrylic acid copolymer resin, and 0.5-0.8 parts of stearic acid. The method for preparing the modified nylon elastomer includes the following steps: The modified nylon elastomer is obtained by mixing nylon elastomer, polyolefin block copolymer, ethylene-methacrylic acid copolymer resin and stearic acid; the mixing temperature is 180~200℃ and the mixing time is 1000~1200s.

2. The elastic composite material according to claim 1, characterized in that, The mixing is carried out in a twin-screw extruder with a main extruder speed of 550~600 r / min.

3. A method for preparing the elastic composite material according to claim 1 or 2, comprising the following steps: The modified nylon elastomer, ethylene vinyl acetate copolymer, stearic acid and zinc oxide were first compounded to obtain the first compound system. The first mixing system, di-tert-butyl peroxide, and foaming agent are mixed a second time to obtain the elastic composite material.

4. The preparation method according to claim 3, characterized in that, The temperature of the first mixing process is 95~100℃ and the time is 600~700s; the temperature of the second mixing process is 110~115℃ and the time is 700~750s.

5. The application of the elastic composite material according to claim 1 or 2 or the elastic composite material prepared by the preparation method according to any one of claims 3 to 4 in shoe soles.

6. An elastic shoe sole, obtained by sequentially foaming, shaping and molding the elastic composite material as described in claim 1 or 2 or the elastic composite material prepared by the preparation method described in any one of claims 3 to 4.

7. The elastic sole according to claim 6, characterized in that, The foaming temperature is 175~180℃ and the time is 500~550s.