技术领域Technical Field
本发明涉及发泡聚氨酯技术领域，尤其涉及一种耐磨PU发泡鞋底及其制备工艺。The invention relates to the technical field of foamed polyurethane, in particular to a wear-resistant PU foamed sole and a preparation process thereof.
背景技术Background Art
PU发泡鞋底，即聚氨酯发泡鞋底，是一种高分子合成材料，具有轻质、耐磨、耐折、弹性好、强度高、耐挠曲等优点。PU发泡鞋底不仅穿着舒适，能有效减轻足部疲劳，还具备良好的吸震性，适用于运动鞋、休闲鞋、劳保鞋等多种鞋类。此外，PU材料环保且易于水解，通过调整配方还可赋予其防酸碱、耐油、防老化、抗水解等特性，以满足不同需求。PU发泡鞋底的生产通常采用发泡工艺，通过将聚氨酯树脂与异氰酸酯等原料混合，加入各种添加剂，然后进行发泡成型，这种工艺可以精确控制鞋底的密度和硬度，以满足不同鞋类的需求。PU发泡鞋底以其优异的性能、广泛的应用和环保特性，成为现代鞋类制造中不可或缺的材料之一。PU foam soles, also known as polyurethane foam soles, are a type of polymer synthetic material with the advantages of being lightweight, wear-resistant, fold-resistant, elastic, strong, and flex-resistant. PU foam soles are not only comfortable to wear and can effectively reduce foot fatigue, but also have good shock absorption properties, making them suitable for a variety of footwear such as sports shoes, casual shoes, and work shoes. In addition, PU materials are environmentally friendly and easily hydrolyzed. By adjusting the formula, they can also be given acid and alkali resistance, oil resistance, aging resistance, and hydrolysis resistance to meet different needs. The production of PU foam soles usually adopts a foaming process, which involves mixing polyurethane resin with raw materials such as isocyanate, adding various additives, and then foaming and molding. This process can precisely control the density and hardness of the sole to meet the needs of different types of footwear. PU foam soles have become one of the indispensable materials in modern footwear manufacturing due to their excellent performance, wide application, and environmental protection characteristics.
聚氨酯弹性体的磨耗性能由材料内外多种因素共同决定，除受本身的强度、滞后性能、弹性模量、疲劳性等内因影响外，还受到温度、压力、滑动速度等外在因素的影响。拉伸强度越高，耐磨性能越好。硬度和定伸应力对弹性体耐磨性的影响视不同的磨耗类型而异。硬度和定伸应力高时，弹性体抗形变能力强，这使摩擦面上的微凸体较难压入基体中，摩擦系数小；此外，弹性体表面刚性越大，不易打皱而引起卷曲，较难发生磨粒磨耗和卷曲磨耗，弹性体磨耗速率减慢，磨耗强度降低，但疲劳磨耗条件下，情况相反。此外，粘弹性参数对弹性体摩擦力有直接的影响，粘弹性参数越大，橡胶交联度会越低，发生磨耗时摩擦力增加，导致磨耗体积增加。而提高耐疲劳性能对降低疲劳磨耗强度有利。耐疲劳性能的改善可以增强弹性体抵抗摩擦引起的表层伸张破坏的能力，导致磨耗图纹出现的时间后移。在疲劳磨耗的情况下，滞后损失增大，使摩擦系数、温升增大，导致弹性体耐磨性能降低。The wear properties of polyurethane elastomers are determined by a variety of factors, both internal and external. In addition to internal factors such as strength, hysteresis, elastic modulus, and fatigue resistance, they are also influenced by external factors such as temperature, pressure, and sliding speed. Higher tensile strength indicates better wear resistance. The effects of hardness and modulus on the wear resistance of elastomers vary depending on the type of wear. High hardness and modulus increase the elastomer's resistance to deformation, making it more difficult for the micro-asperities on the friction surface to press into the matrix, resulting in a lower coefficient of friction. Furthermore, greater surface rigidity reduces the tendency for wrinkling and curling, making abrasive and curling wear less likely to occur. This slows the wear rate and reduces the wear intensity. However, the opposite is true under fatigue wear conditions. Furthermore, the viscoelastic parameters directly influence the friction of the elastomer. Higher viscoelastic parameters indicate a lower degree of crosslinking in the rubber, increasing friction and the wear volume during wear. Improving fatigue resistance, on the other hand, helps reduce fatigue wear intensity. Improved fatigue resistance can enhance the elastomer's ability to resist surface tensile damage caused by friction, causing the wear pattern to appear later. In the case of fatigue wear, hysteresis loss increases, increasing the friction coefficient and temperature rise, resulting in a decrease in the elastomer's wear resistance.
专利号87108373涉及一种新型呋喃多元醇，其核心特征在于该多元醇由以下成分构成：含有多元醇、单元胺或多元胺基团的化合物。这些化合物可以包含呋喃环，也可以与由有机环氧化合物构成的链增长剂混合。当多元醇本身不含呋喃环时，所使用的有机环氧化合物必须为呋喃环氧乙烷。此外，若链增长剂不含某种呋喃环，则不能单独使用2,5-双羟基呋喃。这些呋喃多元醇的主要用途是制备具有改良性质的聚氨酯泡沫，从而提升其性能或优化其特性。CN116622050A涉及一种低密度、耐磨防滑的聚氨酯鞋底树脂，属于聚氨酯弹性体技术领域。该发明的树脂由A组分、B组分和催化剂组成，其中A组分包含70至90份多元醇P1、10至30份多元醇P2、5至15份扩链剂、1至10份耐磨剂、0.5至1.0份硅油和0.4至0.8份发泡剂，且多元醇P1和P2的质量份数之和为100份；B组分则包含25至40份多元醇P1、0至5份多元醇I1和55至75份异氰酸酯。催化剂的加入量为A组分质量的1.5%至2.5%。该树脂制品具有低密度、低DIN磨耗值，以及优异的耐磨性和防滑性能。该发明还提供了该树脂的制备方法和应用。Patent No. 87108373 relates to a novel furan polyol, the core feature of which is that the polyol is composed of the following components: a compound containing a polyol, a monoamine, or a polyamine group. These compounds may contain a furan ring or may be mixed with a chain extender composed of an organic epoxy compound. When the polyol itself does not contain a furan ring, the organic epoxy compound used must be furan oxirane. In addition, if the chain extender does not contain a certain furan ring, 2,5-dihydroxyfuran cannot be used alone. The main use of these furan polyols is to prepare polyurethane foams with improved properties, thereby enhancing their performance or optimizing their characteristics. CN116622050A relates to a low-density, wear-resistant and non-slip polyurethane sole resin, belonging to the field of polyurethane elastomer technology. The resin of the invention consists of component A, component B and a catalyst, wherein component A contains 70 to 90 parts of polyol P1, 10 to 30 parts of polyol P2, 5 to 15 parts of chain extender, 1 to 10 parts of anti-wear agent, 0.5 to 1.0 parts of silicone oil and 0.4 to 0.8 parts of foaming agent, and the sum of the mass parts of polyol P1 and P2 is 100 parts; component B contains 25 to 40 parts of polyol P1, 0 to 5 parts of polyol I1 and 55 to 75 parts of isocyanate. The amount of catalyst added is 1.5% to 2.5% of the mass of component A. The resin product has low density, low DIN wear value, and excellent wear resistance and anti-slip properties. The invention also provides a preparation method and application of the resin.
鞋底材料是一类重要的弹性体材料。随着材料的进步，针对特殊用途开发高耐磨、高耐油、质轻、弹性好、强度高、抗静电、减震效果等等优良的工程鞋底材料具有重要的现实意义和实用价值。Shoe sole materials are an important type of elastomeric material. With the advancement of materials, the development of high-quality engineered shoe sole materials with high wear resistance, high oil resistance, lightweight, good elasticity, high strength, antistatic properties, and shock absorption for special applications has important practical significance and value.
发明内容Summary of the Invention
有鉴于现有技术的上述缺陷，本发明所要解决的技术问题是提供了一种耐磨PU发泡鞋底及其制备工艺。In view of the above-mentioned defects in the prior art, the technical problem to be solved by the present invention is to provide a wear-resistant PU foam sole and a preparation process thereof.
鞋底作为一种经常遭受磨损的材料，其耐磨性好坏直接影响到鞋子的使用寿命。并且，耐磨性好的鞋底材料能够更好地保持缓冲及减震、抓地等性能。因此，提高聚氨酯发泡鞋底材料的耐磨损性能十分必要。As a material that is frequently subject to wear and tear, the wear resistance of shoe soles directly impacts the lifespan of the shoe. Furthermore, sole materials with excellent wear resistance can better maintain cushioning, shock absorption, and grip. Therefore, improving the wear resistance of polyurethane foam sole materials is essential.
本发明提供了一种耐磨PU发泡鞋底，首先制备得到聚呋喃多元醇再与异氰酸酯、扩链剂经水发泡得到鞋底材料，由于呋喃基团具有芳香性，这使得其在聚氨酯中提供了额外的刚性和稳定性。这种刚性结构可以限制分子链的运动，从而减少摩擦和磨损，呋喃基团的芳香性还增强了分子间的作用力，如π-π相互作用和氢键，这些作用力可以提高材料的机械强度和耐磨性。所得到发泡材料由于硬段和软段分布更加均匀，这种均匀的分布有助于提高材料的整体机械性能，包括耐磨性，因此所制备得到聚氨酯发泡材料的耐磨损性能更好，而这一性能的提升对于延长鞋底材料的寿命、保持鞋底材料性能至关重要。The present invention provides a wear-resistant polyurethane (PU) foamed sole. Polyfuran polyol is first prepared and then foamed with isocyanate and a chain extender in water to obtain a sole material. The aromaticity of the furan group provides additional rigidity and stability in the polyurethane. This rigid structure can restrict the movement of the molecular chain, thereby reducing friction and wear. The aromaticity of the furan group also enhances intermolecular forces, such as π-π interactions and hydrogen bonds, which can improve the mechanical strength and wear resistance of the material. The resulting foamed material has a more uniform distribution of hard and soft segments, which helps improve the overall mechanical properties of the material, including wear resistance. Therefore, the prepared polyurethane foam material has better wear resistance, and this improved performance is crucial for extending the life of the sole material and maintaining its performance.
鞋底的使用环境较为复杂，因此耐磨性不是决定其寿命的唯一因素，耐油的鞋底材料能够抵抗油脂的侵蚀，减少因油脂引起的损坏，同样能够延长鞋底的使用寿命。当本发明的鞋底材料具备强极性基团时，所制备得到的鞋底还能够具备较好的耐油性，使得其应用范围更广。The use environment of shoe soles is relatively complex, so wear resistance is not the only factor that determines their lifespan. Oil-resistant sole materials can resist the erosion of grease, reduce damage caused by grease, and also extend the service life of the soles. When the sole material of the present invention has strong polar groups, the prepared soles can also have good oil resistance, which expands its application range.
本发明通过制备得到聚呋喃多元醇再与异氰酸酯、扩链剂、助剂等混合，经水发泡、脱模、熟化得到PU发泡鞋底，所制备的发泡材料具备轻质、高弹、减震等特性，聚呋喃多元醇中呋喃基团的引入能够提供额外的刚性和稳定性，从而提升材料的强度、韧性及抗磨损效果，抗氧剂的加入则能够防止材料老化、变色，润滑剂的加入则能够降低弹性体和界面的摩擦系数，填料作为重要的补强材料，则能够降低摩擦力，因此最终得到的鞋底具备耐磨、耐油、减震、抗缓冲等多重性能，且具备更长的使用寿命。The present invention prepares polyfuran polyol, mixes the mixture with isocyanate, chain extender, auxiliary agent and the like, and performs water foaming, demoulding and aging to obtain a PU foamed sole. The prepared foamed material has the characteristics of light weight, high elasticity and shock absorption. The introduction of furan groups in the polyfuran polyol can provide additional rigidity and stability, thereby improving the strength, toughness and wear resistance of the material. The addition of antioxidants can prevent aging and discoloration of the material. The addition of lubricants can reduce the friction coefficient of the elastomer and the interface. Fillers, as important reinforcing materials, can reduce friction. Therefore, the final obtained sole has multiple properties such as wear resistance, oil resistance, shock absorption and anti-buffering, and has a longer service life.
为实现上述目的，本发明提供了一种耐磨PU发泡鞋底的制备工艺，包括如下步骤：To achieve the above object, the present invention provides a preparation process for a wear-resistant PU foam sole, comprising the following steps:
S1、将双-(5-羧基糠基)醚与多元醇在惰性气氛下升温至140~150℃混合，搅拌6~10h后加入3-氨基己二酸，继续升温至160~180℃，搅拌20~30h后加入二月桂酸二丁基锡，聚合48~72h结束后干燥得到聚呋喃多元醇；S1. Bis-(5-carboxyfurfuryl) ether and polyol are heated to 140-150° C. under an inert atmosphere, stirred for 6-10 hours, and then 3-aminoadipic acid is added. The temperature is further raised to 160-180° C., stirred for 20-30 hours, and then dibutyltin dilaurate is added. After polymerization for 48-72 hours, the mixture is dried to obtain polyfuran polyol.
S2、将聚呋喃多元醇与六亚甲基二异氰酸酯、1,4-丁二醇、水、二月桂酸二丁基锡以及胺类催化剂、助剂混合后，注入模温为40~50℃的鞋模中，固化发泡3~5min脱模经熟化即得耐磨PU发泡鞋底。S2. Mix polyfuran polyol with hexamethylene diisocyanate, 1,4-butanediol, water, dibutyltin dilaurate, amine catalyst and additives, and inject into a shoe mold with a mold temperature of 40-50°C. Curing and foaming for 3-5 minutes, demolding and aging to obtain a wear-resistant PU foam sole.
进一步的，所述多元醇为2,6-二羟基己腈，1,5-戊二醇或者1,6-己二醇中的一种。Furthermore, the polyol is one of 2,6-dihydroxycapronitrile, 1,5-pentanediol or 1,6-hexanediol.
进一步的，所述胺类催化剂为三乙烯二胺。Furthermore, the amine catalyst is triethylenediamine.
进一步的，所述助剂为抗氧剂、润滑剂、填料混合。Furthermore, the auxiliary agent is a mixture of an antioxidant, a lubricant, and a filler.
进一步的，所述熟化温度为80~90℃。Furthermore, the aging temperature is 80-90°C.
进一步的，所述耐磨PU发泡鞋底的制备工艺，包括如下步骤，以重量份计：Furthermore, the preparation process of the wear-resistant PU foam sole comprises the following steps, calculated in parts by weight:
S1、将双-(5-羧基糠基)醚1份与多元醇2~3份在惰性气氛下升温至140~150℃混合，搅拌6~10h后加入3-氨基己二酸2~3份，继续升温至160~180℃，搅拌20~30h后加入二月桂酸二丁基锡0.001~0.005份，聚合48~72h结束后干燥得到聚呋喃多元醇，双-(5-羧基糠基)醚作为起始原料与多元醇反应形成酯键，所得到的产物继续和3-氨基己二酸反应形成酯键，二月桂酸二丁基锡作为催化剂催化反应进程，最终经聚合得到聚呋喃多元醇；S1, 1 part of bis-(5-carboxyfurfuryl) ether and 2~3 parts of polyols are warming up to 140~150 ℃ of mixing under inert atmosphere, after stirring for 6~10h, 2~3 parts of 3-aminoadipic acid are added, continue to be warming up to 160~180 ℃, after stirring for 20~30h, 0.001~0.005 part of dibutyltin dilaurate is added, after polymerization for 48~72h finishes, drying obtains polyfuran polyol, bis-(5-carboxyfurfuryl) ether forms ester bond with polyol reaction as starting raw material, resulting product continues to react with 3-aminoadipic acid to form ester bond, dibutyltin dilaurate is as catalyst catalyzed reaction process, finally obtains polyfuran polyol through polymerization;
S2、将聚呋喃多元醇100~150份与六亚甲基二异氰酸酯30~40份、1,4-丁二醇3~4份、水1~2份、二月桂酸二丁基锡0.2~0.3份以及胺类催化剂0.1~0.2份、助剂1~2份混合后，注入模温为40~50℃的鞋模中，固化发泡3~5min脱模经80~90℃熟化即得耐磨PU发泡鞋底。S2. Mix 100-150 parts of polyfuran polyol, 30-40 parts of hexamethylene diisocyanate, 3-4 parts of 1,4-butanediol, 1-2 parts of water, 0.2-0.3 parts of dibutyltin dilaurate, 0.1-0.2 parts of amine catalyst, and 1-2 parts of auxiliary agent, and inject the mixture into a shoe mold at a mold temperature of 40-50°C. Curing and foaming for 3-5 minutes, demolding, and aging at 80-90°C to obtain a wear-resistant PU foam sole.
优选的，所述抗氧剂为抗氧剂1076。Preferably, the antioxidant is antioxidant 1076.
优选的，所述润滑剂为硬脂酸锌。Preferably, the lubricant is zinc stearate.
优选的，所述填料为白炭黑。Preferably, the filler is white carbon black.
优选的，所述助剂中抗氧剂、润滑剂及填料的质量比为0.1~0.5:0.1~0.3:1~2。Preferably, the mass ratio of the antioxidant, lubricant and filler in the auxiliary agent is 0.1~0.5:0.1~0.3:1~2.
本发明还提供了一种耐磨PU发泡鞋底，由上述方法制备而成。The present invention also provides a wear-resistant PU foam sole, which is prepared by the above method.
本发明的有益效果：Beneficial effects of the present invention:
1、与现有技术相比，本发明提供了一种耐磨PU发泡鞋底，首先制备得到聚呋喃多元醇再与异氰酸酯、扩链剂经水发泡得到鞋底材料，由于呋喃基团具有芳香性，这使得其在聚氨酯中提供了额外的刚性和稳定性。这种刚性结构可以限制分子链的运动，从而减少摩擦和磨损，因此所制备得到聚氨酯发泡材料的耐磨损性能更好。Compared to the prior art, the present invention provides a wear-resistant PU foam sole. Polyfuran polyol is first prepared and then foamed with isocyanate and a chain extender in water to produce the sole material. The aromatic nature of the furan group provides additional rigidity and stability within the polyurethane. This rigid structure restricts the movement of the molecular chains, thereby reducing friction and wear. Consequently, the resulting polyurethane foam material exhibits improved wear resistance.
2、相比现有技术，本发明得到的鞋底具备耐磨、耐油、减震、抗缓冲等多重性能，且具备更长的使用寿命。2. Compared with the existing technology, the sole obtained by the present invention has multiple properties such as wear resistance, oil resistance, shock absorption, and anti-buffering, and has a longer service life.
具体实施方式DETAILED DESCRIPTION
双-(5-羧基糠基)醚，CAS号：76154-25-1。Bis-(5-carboxyfurfuryl) ether, CAS number: 76154-25-1.
抗氧剂1076，来源于巴斯夫。Antioxidant 1076, sourced from BASF.
聚醚多元醇，型号：PPG-3000，来源于陶氏。Polyether polyol, model: PPG-3000, from Dow.
实施例1Example 1
一种耐磨PU发泡鞋底的制备工艺，包括如下步骤，以重量份计：A preparation process for a wear-resistant PU foam sole comprises the following steps, calculated in parts by weight:
S1、将双-(5-羧基糠基)醚1份与1,5-戊二醇2.6份在氮气气氛下升温至145℃混合，搅拌8h后加入3-氨基己二酸2.8份，继续升温至170℃，搅拌24h后加入二月桂酸二丁基锡0.003份，聚合60h结束后干燥得到聚呋喃多元醇；S1. Mix 1 part of bis-(5-carboxyfurfuryl) ether and 2.6 parts of 1,5-pentanediol at 145° C. under a nitrogen atmosphere, stir for 8 h, add 2.8 parts of 3-aminoadipic acid, continue heating to 170° C., stir for 24 h, add 0.003 parts of dibutyltin dilaurate, and polymerize for 60 h before drying to obtain polyfuran polyol.
S2、将聚呋喃多元醇125份与六亚甲基二异氰酸酯35份、1,4-丁二醇3.5份、水1.5份、二月桂酸二丁基锡0.25份以及三乙烯二胺0.15份、抗氧剂1076 0.3份、硬脂酸锌0.2份、白炭黑1份混合后，注入模温为45℃的鞋模中，固化发泡4min脱模经85℃熟化24h，即得耐磨PU发泡鞋底。S2. Mix 125 parts of polyfuran polyol with 35 parts of hexamethylene diisocyanate, 3.5 parts of 1,4-butanediol, 1.5 parts of water, 0.25 parts of dibutyltin dilaurate, 0.15 parts of triethylenediamine, 0.3 parts of antioxidant 1076, 0.2 parts of zinc stearate, and 1 part of white carbon black, and inject the mixture into a shoe mold at a mold temperature of 45°C. The mixture is cured and foamed for 4 minutes, demolded, and aged at 85°C for 24 hours to obtain a wear-resistant PU foam sole.
实施例2Example 2
与实施例1基本相同，唯一区别在于将1,5-戊二醇替换为1,6-己二醇。The process is basically the same as Example 1, except that 1,5-pentanediol is replaced by 1,6-hexanediol.
实施例3Example 3
与实施例1基本相同，唯一区别在于将1,5-戊二醇替换为2,6-二羟基己腈。The process is basically the same as Example 1, except that 1,5-pentanediol is replaced by 2,6-dihydroxyhexanenitrile.
对照例1Comparative Example 1
一种耐磨PU发泡鞋底的制备工艺，包括如下步骤，以重量份计：A preparation process for a wear-resistant PU foam sole comprises the following steps, calculated in parts by weight:
将聚醚多元醇125份与六亚甲基二异氰酸酯35份、1,4-丁二醇3.5份、水1.5份、二月桂酸二丁基锡0.25份以及三乙烯二胺0.15份、抗氧剂1076 0.3份、硬脂酸锌0.2份、白炭黑1份混合后，注入模温为45℃的鞋模中，固化发泡4min脱模经85℃熟化24h即得耐磨PU发泡鞋底。125 parts of polyether polyol were mixed with 35 parts of hexamethylene diisocyanate, 3.5 parts of 1,4-butanediol, 1.5 parts of water, 0.25 parts of dibutyltin dilaurate, 0.15 parts of triethylenediamine, 0.3 parts of antioxidant 1076, 0.2 parts of zinc stearate and 1 part of white carbon black, and then injected into a shoe mold at a mold temperature of 45°C. The mixture was cured and foamed for 4 minutes, demolded and aged at 85°C for 24 hours to obtain a wear-resistant PU foam sole.
对照例2Comparative Example 2
一种耐磨PU发泡鞋底的制备工艺，包括如下步骤，以重量份计：A preparation process for a wear-resistant PU foam sole comprises the following steps, calculated in parts by weight:
S1、将双-(5-羧基糠基)醚1份与1,5-戊二醇2.6份在氮气气氛下升温至145℃混合，搅拌8h后加入己二酸2.8份，继续升温至170℃，搅拌24h后加入二月桂酸二丁基锡0.003份，聚合60h结束后干燥得到聚呋喃多元醇；S1. Mix 1 part of bis-(5-carboxyfurfuryl) ether and 2.6 parts of 1,5-pentanediol at 145° C. under a nitrogen atmosphere, stir for 8 h, add 2.8 parts of adipic acid, continue heating to 170° C., stir for 24 h, add 0.003 parts of dibutyltin dilaurate, and polymerize for 60 h before drying to obtain polyfuran polyol;
S2、将聚呋喃多元醇125份与六亚甲基二异氰酸酯35份、1,4-丁二醇3.5份、水1.5份、二月桂酸二丁基锡0.25份以及三乙烯二胺0.15份、抗氧剂1076 0.3份、硬脂酸锌0.2份、白炭黑1份混合后，注入模温为45℃的鞋模中，固化发泡4min脱模经85℃熟化24h即得耐磨PU发泡鞋底。S2. Mix 125 parts of polyfuran polyol with 35 parts of hexamethylene diisocyanate, 3.5 parts of 1,4-butanediol, 1.5 parts of water, 0.25 parts of dibutyltin dilaurate, 0.15 parts of triethylenediamine, 0.3 parts of antioxidant 1076, 0.2 parts of zinc stearate, and 1 part of white carbon black, and inject the mixture into a shoe mold at a mold temperature of 45°C. The mixture is cured and foamed for 4 minutes, demolded, and aged at 85°C for 24 hours to obtain a wear-resistant PU foam sole.
测试例1Test Example 1
对实施例和对照例所制备的PU发泡鞋底进行力学性能的测试，包括拉伸强度、断裂伸长率和撕裂强度；The mechanical properties of the PU foam soles prepared in the examples and the control examples were tested, including tensile strength, elongation at break, and tear strength;
其中，拉伸强度、断裂伸长率的测试参考GB/T1040.1-2018《塑料 拉伸性能的测定第1部分：总则》中的方法进行测试，撕裂强度的测试参考GB/T 3903.12-2021《鞋类 外底试验方法 撕裂强度》中的方法进行测试。Among them, the tests of tensile strength and elongation at break are carried out with reference to the methods in GB/T1040.1-2018 "Plastics - Determination of tensile properties - Part 1: General principles", and the test of tear strength is carried out with reference to the methods in GB/T 3903.12-2021 "Footwear - Outsole Test Method - Tear Strength".
表1Table 1
从表1可以看到，本发明所制备的PU发泡鞋底材料具备较好的力学性能，聚氨酯发泡材料由于具有独特的泡孔结构，而这种结构则能够提供良好的支撑和缓冲，在受到外力作用时，泡孔能够发生变形，吸收和耗散能量，从而起到缓冲和减震的作用。As can be seen from Table 1, the PU foam sole material prepared in the present invention has good mechanical properties. The polyurethane foam material has a unique pore structure, which can provide good support and cushioning. When subjected to external force, the pores can deform, absorb and dissipate energy, thereby playing a role in cushioning and shock absorption.
实施例和对照例1相比，对照例1采用聚醚多元醇作为软段，而实施例采用聚呋喃多元醇作为软段，在聚氨酯材料中。软段是聚氨酯结构中的柔软部分，具有柔软、弯曲和可拉伸的性能，在聚氨酯泡沫中起到增强材料柔性和弹性的作用。硬段则是聚氨酯结构中的刚性部分，具有较高的强度、硬度和耐磨损性。实施例中通过制备得到聚呋喃多元醇再与异氰酸酯、扩链剂经水发泡得到鞋底材料，由于呋喃基团具有芳香性，这使得其在聚氨酯中提供了额外的刚性和稳定性。这种刚性结构可以限制分子链的运动，从而减少摩擦和磨损，呋喃基团的芳香性还增强了分子间的作用力，如π-π相互作用和氢键，这些作用力可以提高材料的机械强度。并且，实施例中所得到发泡材料硬段和软段分布更加均匀，这种均匀的分布有助于提高材料的整体机械性能。The embodiment is compared with reference example 1, and reference example 1 adopts polyether polyol as soft segment, while the embodiment adopts polyfuran polyol as soft segment in polyurethane material.Soft segment is the soft part in the polyurethane structure, has softness, bending and stretchable performance, plays the effect of reinforcing material flexibility and elasticity in polyurethane foam.Hard segment is then the rigid part in the polyurethane structure, has higher intensity, hardness and wear resistance.In the embodiment, obtain polyfuran polyol by preparing again with isocyanate, chain extender through water foaming and obtain sole material, because furan group has aromaticity, this makes it provide extra rigidity and stability in polyurethane.This rigid structure can limit the motion of molecular chain, thereby reduces friction and wear, and the aromaticity of furan group also strengthens intermolecular active force, as π-π interaction and hydrogen bond, and these active forces can improve the mechanical strength of material.And, obtained foam material hard segment and soft segment distribution are more even in the embodiment, and this even distribution helps to improve the overall mechanical property of material.
实施例和对照例2相比，在聚呋喃多元醇的制备中加入3-氨基己二酸而非己二酸，而实施例相比对照例2，力学性能也有了一定提升，这可能是由于3-氨基己二酸所具有的氨基能够和聚氨酯中的氨基甲酸酯结构形成额外的氢键，从而提高作用力，使得材料内部的连接更为紧密，因此力学性能有了一定的提升。Compared with Control Example 2, 3-aminoadipic acid was added instead of adipic acid in the preparation of polyfuran polyol in Example 2, and the mechanical properties of Example 2 were also improved to a certain extent. This may be because the amino group of 3-aminoadipic acid can form additional hydrogen bonds with the carbamate structure in the polyurethane, thereby increasing the force and making the connection inside the material tighter, so that the mechanical properties are improved to a certain extent.
本发明所制备的发泡材料具备轻质、高弹、减震等特性，聚呋喃多元醇中呋喃基团的引入能够提供额外的刚性和稳定性，从而提升材料的强度、韧性及抗磨损效果，因此最终得到的鞋底具备耐磨、减震、抗缓冲等多重性能，且具备更长的使用寿命。The foamed material prepared by the present invention has the characteristics of lightness, high elasticity, and shock absorption. The introduction of furan groups in polyfuran polyol can provide additional rigidity and stability, thereby improving the strength, toughness and wear resistance of the material. Therefore, the final sole has multiple properties such as wear resistance, shock absorption, and anti-buffering, and has a longer service life.
测试例2Test Example 2
对实施例和对照例所制备的PU发泡鞋底进行耐磨、耐油的测试，其中耐磨性测试参考ISO4649:2024《硫化橡胶或热塑性橡胶 使用旋转圆柱形滚筒装置测定耐磨性》测定样品体积磨耗量，计算公式如下：𝑉𝑡=(𝑚1−𝑚2)/𝜌×1000，𝑉𝑡代表实验胶的体积磨耗量；m1和m2分别是试验胶磨耗前后的质量；𝜌是实验胶的密度。The PU foam soles prepared in the examples and control examples were tested for wear resistance and oil resistance. The wear resistance test was carried out according to ISO4649:2024 "Rubber, vulcanized or thermoplastic - Determination of wear resistance using a rotating cylindrical roller apparatus" to measure the volume wear of the sample. The calculation formula is as follows: 𝑉𝑡 =(𝑚1 −𝑚2 )/𝜌×1000, where 𝑉𝑡 represents the volume wear of the test rubber; m1 and m2 are the masses of the test rubber before and after wear, respectively; 𝜌 is the density of the test rubber.
耐油性能参考ISO1817:2024《硫化橡胶或热塑性橡胶.耐液体作用的测定》中的方法，测定样品在试验液体中的质量变化率，计算公式如下：∆𝑚100=𝑚𝑖−𝑚0/𝑚0×100%，式中∆𝑚100代表样品浸油后的质量变化率，𝑚0是样品浸油前的质量；𝑚𝑖是样品浸油后的质量。The oil resistance performance refers to the method in ISO1817:2024 "Rubber, vulcanized or thermoplastic. Determination of resistance to the action of liquids". The mass change rate of the sample in the test liquid is determined by the following formula: ∆𝑚100 = 𝑚𝑖 −𝑚0 /𝑚0 × 100%, where ∆𝑚100 represents the mass change rate of the sample after oil immersion, 𝑚0 is the mass of the sample before oil immersion, and 𝑚𝑖 is the mass of the sample after oil immersion.
表2Table 2
鞋底作为一种经常遭受磨损的材料，其耐磨性好坏直接影响到鞋子的使用寿命。并且，耐磨性好的鞋底材料能够更好地保持缓冲及减震、抓地等性能。从表2可以看到，实施例所制备的PU发泡材料具备更低的体积磨耗量，这可能是由于实施例中通过制备得到聚呋喃多元醇再与异氰酸酯、扩链剂经水发泡得到鞋底材料，由于呋喃基团具有芳香性，这使得其在聚氨酯中提供了额外的刚性和稳定性。这种刚性结构可以限制分子链的运动，从而减少摩擦和磨损，呋喃基团的芳香性还增强了分子间的作用力，如π-π相互作用和氢键，这些作用力可以提高材料的机械强度。另外，聚呋喃多元醇的制备中加入3-氨基己二酸，而3-氨基己二酸所具有的氨基能够和聚氨酯中的氨基甲酸酯结构形成额外的氢键，从而提高作用力，使得材料内部的连接更为紧密，更不易磨损。因此，相比较对照例，实施例的体积磨耗量更低。As a material that often suffers from wear and tear, the wear resistance of the sole directly affects the service life of the shoes. And the sole material with good wear resistance can better keep performances such as cushioning and shock absorption, gripping. As can be seen from Table 2, the PU foam material prepared by the embodiment possesses lower volumetric wear loss. This may be due to obtaining the sole material through water foaming with isocyanate and chain extender by preparing polyfuran polyol in the embodiment, because the furan group has aromaticity, which makes it provide extra rigidity and stability in polyurethane. This rigid structure can limit the motion of molecular chain, thereby reduces friction and wear, and the aromaticity of the furan group has also strengthened the intermolecular force, as π-π interaction and hydrogen bond, and these forces can improve the mechanical strength of material. In addition, 3-aminoadipic acid is added in the preparation of polyfuran polyol, and the amino group that 3-aminoadipic acid has can form extra hydrogen bond with the carbamate structure in the polyurethane, thereby improving the force, making the connection of material interior tighter, more difficult for wear and tear. Therefore, compared with the reference example, the volumetric wear loss of the embodiment is lower.
在日常生活中，鞋底可能会接触到各种油脂，如汽车油、厨房油等。如果鞋底材料不耐油，油脂会渗透到鞋底内部，导致鞋底膨胀、变形、开裂或失去弹性，从而影响鞋底的性能和外观质量。另外，耐油的鞋底材料能够抵抗油脂的侵蚀，减少因油脂引起的损坏，从而延长鞋底的使用寿命。而质量变化率则能够反映材料在油中的吸油、溶胀或溶解情况。质量增加通常表示材料吸收了油，而质量减少则可能表示材料中的某些成分溶解到了油中。质量变化率越小，说明材料的耐油性能越好。In daily life, shoe soles may come into contact with various oils and fats, such as automotive oil and cooking oil. If the sole material is not oil-resistant, the oil will penetrate into the sole, causing it to swell, deform, crack, or lose elasticity, thus affecting its performance and appearance. Oil-resistant sole materials can also resist the erosion of oil and fat, reducing damage caused by oil and fat, thereby extending the service life of the sole. The mass change rate can reflect the material's absorption, swelling, or dissolution in oil. An increase in mass generally indicates that the material has absorbed the oil, while a decrease in mass may indicate that certain components in the material have dissolved into the oil. The smaller the mass change rate, the better the material's oil resistance.
实施例3与其他实施例及对照例相比，质量变化率更小，这可能是由于实施例3中的多元醇2,6-二羟基己腈具有强极性基团——腈基，强极性使得含有腈基的材料能够与油类分子形成一定的相互作用，从而稳定材料的结构，减少油对材料的侵蚀和溶胀，因此实施例3在油性液体中表现最好，其质量变化率最低。Compared with the other embodiments and the control examples, Example 3 has a smaller mass change rate. This may be because the polyol 2,6-dihydroxyhexanenitrile in Example 3 has a strong polar group - nitrile group. The strong polarity enables the material containing the nitrile group to form a certain interaction with the oil molecules, thereby stabilizing the structure of the material and reducing the erosion and swelling of the material by the oil. Therefore, Example 3 performs best in oily liquids and has the lowest mass change rate.
以上详细描述了本发明的较佳具体实施例。应当理解，本领域的普通技术人员无需创造性劳动就可以根据本发明的构思作出诸多修改和变化。因此，凡本技术领域中技术人员依本发明的构思在现有技术的基础上通过逻辑分析、推理或者有限的实验可以得到的技术方案，皆应在由权利要求书所确定的保护范围内。The above describes in detail the preferred embodiments of the present invention. It should be understood that those skilled in the art can make numerous modifications and variations based on the concepts of the present invention without inventive effort. Therefore, any technical solutions that can be derived by those skilled in the art through logical analysis, reasoning, or limited experimentation based on the concepts of the present invention and the prior art should be within the scope of protection defined by the claims.
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