CN109923138A - 3d间隔织物增强的pu复合材料及其用途 - Google Patents
3d间隔织物增强的pu复合材料及其用途 Download PDFInfo
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Abstract
本发明涉及一种3D间隔织物增强的PU复合材料、其制备方法、其在鞋材(特别是在鞋底)中的用途以及一种鞋材(特别是鞋底),其包含所述复合材料。
Description
技术领域
本发明涉及一种3D间隔织物增强的PU复合材料、其制备方法、其在鞋材(特别是在鞋底)中的用途以及一种鞋材(特别是鞋底),其包含所述复合材料。
背景技术
聚氨酯(PU)泡沫是一种重要的材料且被广泛地用于各个领域。PU泡沫具有优异的性能,例如良好的隔热性能、轻质、高比强度及处理方便等。此外,PU泡沫具有例如热、声及电绝缘性、耐热性及耐溶剂性等特点。因此,PU泡沫被广泛地用于例如作为冰箱及工业设备(例如储存容器及管道)中的绝热材料、作为建筑材料(例如车辆顶棚)以及作为汽车中的内部饰件。
更具体地,由于轻质及耐磨的特性,PU泡沫被用于鞋材作为鞋底。然而,现有技术中已知的PU泡沫具有某些缺点,例如耐磨性差及和撕裂强力低,限制了其在鞋材(尤其是在低密度PU鞋底)中的用途。此外,现有技术中已知的基于聚醚多元醇的PU具有耐磨性差的缺点,使得基于聚醚多元醇的PU很少被用作外底。因此,仍然有进一步改善用作鞋底的PU泡沫的空间。
另一方面,3D间隔织物(也被称为经编(warp-knitted)间隔织物)是由以间隔纱线连接在一起的两个分开的外部织物层所组成的新颖的三维织物。3D间隔织物近来被用于制备3D结构复合材料。由3D间隔织物制成的复合材料具有以下优点:(1)该复合材料可在一个单一步骤中制备,而非通过复杂的制备方法制备;(2)该织物的两个外层被间隔纱线束缚,因此几乎不发生面芯分层(face-core delamination);(3)中空芯可填充各种材料。因此,整体3D结构复合材料被广泛地用于汽车、车辆、船舶等。
Si Chen等人于Mechanical properties of 3d-structure composites basedon warp-knitted spacer fabrics,AUTEX Research Journal,第15卷,第2期,2015年6月,DOI:10.2478/aut-2014-0045,第127-137页公开了通过以PU泡沫浸渍经编间隔织物制备的3D结构复合材料。该文件未公开该PU泡沫的具体组成以及所得到的3D复合材料在鞋材中的用途。实际上,该3D复合材料由于其低机械性能并无法在鞋应用中使用。
Si Chen与Hai-Ru Long于Investigation on compression properties of PU-based warp-knitted spacer fabric composites for cushioning applications,PartI.Experiment,Industria Textilǎ,2014,第65卷,第4期,第200-205页也公开了一种基于PU的经编间隔织物复合材料。该文件也未公开该PU泡沫的具体组成以及所得到的3D复合材料在鞋材中的用途。实际上,由于机械性能(尤其是韧性、伸长率及硬度)不佳,所得组合物并无法在鞋应用中使用。
现有技术并未公开3D间隔织物增强的PU复合材料在鞋材(特别是在鞋底)中的用途。
发明人惊奇地发现,与纯泡沫相比,通过使用特定的PU泡沫与3D间隔织物组合,3D间隔织物增强的PU复合材料显示出改善的机械性能及独特的性能,例如独特的各向异性效应,且因此获得了具有在鞋材应用上极大的潜力。基于此发现,发明人完成了本发明。
发明概述
因此,本发明的目的在于提供一种3D间隔织物增强的PU复合材料。该复合材料显示出改善的机械性能及独特的性能,例如独特的各向异性效应,使其适合用于鞋材,特别是鞋底。
本发明的另一目的在于该3D间隔织物增强的PU复合材料在鞋材(特别是在鞋底)中的用途。
发明详述
一方面,本发明涉及3D间隔织物增强的PU复合材料。
用于本发明的3D间隔织物在现有技术中已经是已知的。该3D间隔织物通常包含第一或顶层材料,其通过间隔纱线与大致平行的第二或底层材料分开。
3D间隔织物通常通过双针床拉舍尔经编机(Raschel warp knitting machine)生产。所述双针床拉舍尔经编机基本上安装有两个独立操作的针床,其通过相应的多个纱线梳栉从多个各自的经轴进给多根纱线。该3D间隔织物通常由分别缠绕在各别经轴上的五组或更多组的经纱线产生,并通过相应的一组纱线梳栉进给至该两个针床,通常具有至少两组通过两个相应的纱线梳栉进给的经纱线被专门地进给至所述针床之一以制造一个打底层,至少其他两组通过其他相应的梳栉进给的经纱线被专门地进给至另一个针床以制备另一个打底层,并且其余的组通过一个或多个剩余的可用的梳栉进给的经纱线被交替地进给至该两个针床以在该两个打底层之间延伸并且与该两个打底层之间进行编织,从而整合及保持打底结构处于间隔基本上平行的关系。
顶层及/或底层可具有各种表面结构,例如链条+垫纱(Chain+Inlay),经平绒针组织(Locknit)或六边形网格(Hexagonal Mesh)。
用于建构3D间隔织物的纤维可由提供所需性质的任何材料制成。通过改变原料,织物的密度及其性能可被量身定做以适合于特定应用。在本发明的上下文中,该织物可由例如聚对苯二甲酸乙二醇酯(PET)、聚对苯二甲酸丁二醇酯(PBT)、尼龙、聚丙烯腈等制成,更优选PET及PBT,最优选PET。当然,该3D间隔织物可由这些材料的任何组合制成并且可进一步包含其他材料。
用于建构3D间隔织物的间隔纱线的直径并非关键,但优选为约0.05-约0.5mm,更优选为约0.10-约0.4mm,甚至更优选为约0.15-约0.3mm,最优选为约0.15-约0.25mm。
此外,已发现间隔纱线的倾角会影响得到的3D间隔织物增强的PU复合材料的机械性能。在本发明的上下文中,“间隔纱线的倾角”定义为间隔纱线相对于织物的顶层或底层的角度。所述角度会影响各向异性效应,没有该角度就没有各向异性效应。间隔纱线的倾角可为约40-约85°,优选为约50-约80°,更优选为约60-约80°,甚至更优选为约65-约80°,最优选为约65-约75°。
该3D间隔织物的厚度可根据实际应用进行优化,尤其根据鞋材的所需厚度,且通常为约2-约15mm,优选为约3-约12mm,更优选为约5-约10mm,最优选为约5.5-约8mm。
本发明所用的PU泡沫通过使下列组分反应而制备:
(a)二异氰酸酯或多异氰酸酯,
(b)聚醚多元醇或聚酯多元醇,和
(c)任选的发泡剂。
所用的二异氰酸酯或多异氰酸酯可为已知用于制备PU的任何脂族、脂环族或芳族异氰酸酯。实例为二苯甲烷2,2′-、2,4-和4,4′-二异氰酸酯,单体型二苯甲烷二异氰酸酯与具有更多环数的二苯甲烷二异氰酸酯同系物(聚合MDI)的混合物,异佛尔酮二异氰酸酯(IPDI)或其低聚物,甲苯二异氰酸酯(TDI),例如甲苯二异氰酸酯异构体如甲苯2,4-或2,6-二异氰酸酯或这些的混合物,四亚甲基二异氰酸酯或其低聚物,六亚甲基二异氰酸酯(HDI)或其低聚物,萘二异氰酸酯(NDI),或其混合物。
所用的二异氰酸酯或多异氰酸酯优选包括基于二苯甲烷二异氰酸酯的异氰酸酯,特别是包括聚合MDI。二异氰酸酯或多异氰酸酯的官能度优选为2.0-2.9,特别优选为2.1-2.8。二异氰酸酯或多异氰酸酯在25℃下根据DIN53019-1至3的粘度优选为约5-约600mPas,特别优选为约10-约300mPas。
二异氰酸酯和多异氰酸酯也可以以多异氰酸酯预聚物的形式使用。这些多异氰酸酯预聚物可通过使过量的上述多异氰酸酯与具有至少两个对异氰酸酯具有反应性的基团的化合物在例如30-100℃,优选约80℃的温度下反应得到预聚物而获得。本发明的多异氰酸酯预聚物的NCO含量优选为10-33重量%的NCO,特别优选为15-25重量%的NCO。
用于制备PU泡沫的聚醚多元醇通过已知方法获得,例如通过在加入至少一种包含2-8个,优选2-6个结合形式的反应性氢原子的起始剂分子下在催化剂存在下阴离子聚合氧化烯而获得。作为催化剂,可使用碱金属氢氧化物如氢氧化钠或氢氧化钾,或碱金属醇盐如甲醇钠、乙醇钠或乙醇钾或异丙醇钾,或者在阳离子聚合的情况下,使用路易斯酸如五氯化锑、三氟化硼醚合物或漂白土作为催化剂。此外,称为DMC催化剂的双金属氰化物化合物也可用作催化剂。
作为氧化烯,优选使用一种或多种在亚烷基中具有2-4个碳原子的化合物,例如氧化乙烯,1,3-氧化丙烯、四氢呋喃、1,2-或2,3-氧化丁烯,在每种情况下单独或呈混合物的形式,优选为氧化乙烯和/或1,2-氧化丙烯。
可能的起始剂分子例如为乙二醇、二甘醇、甘油、三羟甲基丙烷、季戊四醇,糖衍生物如蔗糖,糖醇如山梨醇,甲胺、乙胺、异丙胺、丁胺、苄胺、苯胺、甲苯胺、甲苯二胺、萘胺、乙二胺、二亚乙基三胺、4,4′-亚甲基二苯胺、1,3-丙二胺、1,6-己二胺、乙醇胺、二乙醇胺、三乙醇胺以及其他二元或多元醇,或单官能或多官能胺。
聚酯多元醇通常通过具有2-12个碳原子的多元醇,例如乙二醇、二甘醇、丁二醇、三羟甲基丙烷、甘油或季戊四醇,与具有2-12个碳原子的多元羧酸,例如琥珀酸、戊二酸、己二酸、辛二酸、壬二酸、癸二酸、癸烷二甲酸、马来酸、富马酸、邻苯二甲酸、间苯二甲酸、对苯二甲酸、萘二甲酸的异构体或所述酸的酐缩合而制备。多元羧酸还包括二羧酸的其他源,例如对苯二甲酸二甲酯(DMT)、聚对苯二甲酸乙二醇酯(PET)等。
本文所用的聚醚多元醇或聚酯多元醇具有约1.7-约2.5,优选约1.8-约2.4,更优选约1.8-约2.3的官能度。此外,本文所用的聚醚多元醇或聚酯多元醇具有约50-约270mgKOH/g,优选约55-约200mg KOH/g,更优选约55-约150mg KOH/g,甚至更优选约55-约100mgKOH/g,最优选约55-约80mg KOH/g的羟值。令人惊讶地发现,当聚醚多元醇或聚酯多元醇的官能度和羟值落入上述范围时,获得了具有高机械性能和独特的各向异性效应的3D间隔织物增强的PU复合材料,这使得所述复合材料适合用于鞋材,特别是鞋底。
聚醚多元醇或聚酯多元醇的分子量为约500-约6000,优选为约600-约4000,更优选为约1000-约2500。此外,聚醚多元醇或聚酯多元醇的多分散指数处于特定的范围内,例如约0.8-约1.3,优选约0.9-约1.2,更优选约0.95-约1.1。当处于所述多分散指数范围内时,获得的复合材料在硬度和韧性之间具有最佳平衡。
用于制备PU泡沫的反应混合物可进一步包含交联剂和/或扩链剂。
作为扩链剂和/或交联剂,特别使用例如双官能或三官能的胺和醇,特别是二元醇、三元醇或二者,在每种情况下其分子量小于350,优选为60-300,特别为60-250。此处,双官能化合物称为扩链剂,而三官能或更高官能的化合物称为交联剂。可使用例如具有2-14个,优选2-10个碳原子的脂族、脂环族和/或芳族二元醇,例如乙二醇、1,2-丙二醇、1,3-丙二醇、1,2-戊二醇、1,3-戊二醇、1,10-癸烷二醇、1,2-二羟基环己烷、1,3-二羟基环己烷、1,4-二羟基环己烷、二甘醇和三甘醇、二丙二醇和三丙二醇、1,4-丁二醇、1,6-己二醇和双(2-羟基乙基)氢醌;三元醇,例如1,2,4-三羟基环己烷、1,3,5-三羟基环己烷、甘油和三羟甲基丙烷;以及基于氧化乙烯和/或1,2-氧化丙烯以及上述二元醇和/或三元醇作为起始剂分子的含羟基的低分子量聚氧化烯。
扩链剂可为单独的化合物或混合物。扩链剂优选包括丙二醇、二丙二醇、三丙二醇和/或2,3-丁二醇,单独或者任选呈彼此的混合物或与其他扩链剂的混合物的形式。因此,在特别优选的实施方案中,二丙二醇与第二扩链剂如2,3-丁二醇、单丙二醇或二甘醇一起用作扩链剂。
交联剂优选为1,2,4-三羟基环己烷、1,3,5-三羟基环己烷、甘油和/或三羟甲基丙烷。优选使用甘油作为交联剂。
用于制备所述PU泡沫的反应混合物可进一步包含发泡剂。所述发泡剂可为物理发泡剂或化学发泡剂。
物理发泡剂为对起始组分呈惰性且通常在室温下为液态,而在氨基甲酸酯反应条件下蒸发的化合物。这些化合物的沸点优选低于50℃。物理发泡剂还包括在室温下为气态且在压力下引入或溶解在起始组分中的化合物,例如二氧化碳、低沸点链烷烃、氟代链烷烃和氟代烯烃。
物理发泡剂通常选自具有至少4个碳原子的链烷烃和环烷烃,二烷基醚,酯,酮,缩醛,氟代链烷烃,氟代烯烃,具有1-8个碳原子,和在烷基链中具有1-3个碳原子的四烷基硅烷,特别是四甲基硅烷。
可提及的实例为丙烷、正丁烷、异丁烷和环丁烷、正戊烷、异戊烷和环戊烷、环己烷、二甲醚、甲基乙基醚、甲基丁基醚、甲酸甲酯、丙酮和可在对流层中降解且因此不会破坏臭氧层的氟代链烷烃,例如三氟甲烷、二氟甲烷、1,1,1,3,3-五氟丁烷、1,1,1,3,3-五氟丙烷、1,1,1,2-四氟乙烷、二氟乙烷和七氟丙烷。氟代烯烃的实例为1-氯-3,3,3-三氟丙烯、1,1,1,4,4,4-六氟丁烯。所提及的物理发泡剂可单独使用或以彼此的任意组合使用。优选使用1,1,1,3,3-五氟丙烷(以HFC-245fa由Honeywell International Inc.获得)、1-氯-3,3,3-三氟丙烯(以HCFO-LBA2由Honeywell International Inc.获得或者以AFA-L1由ArkemaSA获得)、1,1,1,4,4,4-六氟丁烯(以HFO FEA1100由Dupont获得)。
物理发泡剂(c)的用量使得PU泡沫的密度在不考虑增强材料的情况下优选为约75-约150kg/m3,更优选为约90-约130kg/m3,最优选为约100-约110kg/m3。
作为化学发泡剂,可使用水和/或甲酸。这些与异氰酸酯基团反应,从而分别消去二氧化碳或二氧化碳和一氧化碳。在一个实施方案中,优选使用水作为发泡剂。水的量优选为0.1-2.0重量%,基于反应混合物的重量。
根据本发明,形成PU泡沫的反应在催化剂(d)存在下进行。
作为催化剂(d),可使用促进异氰酸酯-多元醇反应的所有化合物。该类化合物是已知的并且描述于例如“Kunststoffhandbuch,第7卷,PU”,Carl Hanser Verlag,第3版,1993年,第3.4.1章中。这些包括基于胺的催化剂和基于有机金属化合物的催化剂。
作为基于有机金属化合物的催化剂,可使用例如有机锡化合物,例如有机羧酸的锡(II)盐如乙酸锡(II)、辛酸锡(II)、乙基己酸锡(II)和月桂酸锡(II),和有机羧酸的二烷基锡(IV)盐如二乙酸二丁基锡、二月桂酸二丁基锡、马来酸二丁基锡和二乙酸二辛基锡,以及羧酸铋如新癸酸铋(III)、2-乙基己酸铋和辛酸铋,或羧酸的碱金属盐如乙酸钾或甲酸钾。
优选使用叔胺或包含至少一种叔胺的混合物作为催化剂(d)。这些叔胺通常为也可带有对异氰酸酯具有反应性的基团如OH、NH或NH2基的化合物。一些最常用的催化剂为双(2-二甲氨基乙基)醚、N,N,N,N,N-五甲基二亚乙基三胺、N,N,N-三乙氨基乙氧基乙醇、二甲基环己胺、二甲基苄胺、三乙胺、三亚乙基二胺、五甲基二亚丙基三胺、二甲基乙醇胺、N-甲基咪唑、N-乙基咪唑、四甲基六亚甲基二胺、三(二甲氨基丙基)六氢三嗪、二甲氨基丙胺、N-乙基吗啉、二氮杂双环十一碳烯和二氮杂双环壬烯。
根据本发明,形成PU泡沫的反应在一种或多种泡沫稳定剂(e)的存在下进行。
术语泡沫稳定剂是指在泡沫形成期间促进形成规整泡孔结构的物质。可提及的实例为:含硅泡沫稳定剂,例如硅氧烷-氧化烯共聚物和其他有机聚硅氧烷。也可使用脂肪醇、羰基合成醇、脂肪胺、烷基酚、二烷基酚、烷基甲酚、烷基间苯二酚、萘酚、烷基萘酚、萘胺、苯胺、烷基苯胺、甲苯胺、双酚A、烷基化双酚A、聚乙烯醇的烷氧基化产物;以及甲醛和烷基酚,甲醛和二烷基酚,甲醛和烷基甲酚,甲醛和烷基间苯二酚,甲醛和苯胺,甲醛和甲苯胺,甲醛和萘酚,甲醛和烷基萘酚以及甲醛和双酚A的缩合产物的烷氧基化产物,或者这些泡沫稳定剂中两种或更多种的混合物。
泡沫稳定剂的用量优选为约0.5-约4重量%,特别优选为约1-约3重量%,基于PU泡沫的总重量。
在一个实施方案中,形成PU泡沫的反应在其他添加剂和/或助剂(f)的存在下进行。
可使用的助剂和/或添加剂是本身已知用于该目的的物质,例如表面活性剂、泡沫稳定剂、泡孔调节剂、填料、颜料、染料、抗氧化剂、水解稳定剂、抗静电剂、杀真菌剂和抑菌剂。
就用于实施本发明方法的起始物质、发泡剂、催化剂以及助剂和/添加剂而言的进一步细节参见例如Kunststoffhandbuch[塑料手册],第7卷,“PU”,Carl-Hanser-VerlagMunich,1966年第1版,1983年第2版,1993年第3版。
PU泡沫在制备增强材料的过程中原位形成。
本发明的3D间隔织物增强的PU复合材料具有相对于未增强的PU泡沫而言改善的机械性能。更特别地,本发明的3D间隔织物增强的PU复合材料具有改善的拉伸强度,特别是大大改善的撕裂强度。
更重要的是,本发明的3D间隔织物增强的PU复合材料具有独特的各向异性。在本发明的上下文中,“各向异性”旨在表示3D间隔织物增强的PU复合材料在不同方向上具有不同的性质。例如,垂直于间隔纱线的方向的机械性能优于垂直于其的其他两个方向的机械性能。
上述改善的机械性能和各向异性使得本发明的3D间隔织物增强的PU复合材料可用于鞋材,特别是用于鞋底。改善的机械性能延长了鞋底的寿命,各向异性有助于使脚踝在行走或跑步时保持稳定和舒适。该复合材料的外观也允许自由设计鞋子。
在另一方面,本发明涉及一种制备本发明的3D间隔织物增强的PU复合材料的方法,其包括将3D间隔织物和PU复合材料的起始物质添加至模具中,然后发泡。
在添加到模具之前,首先用混合装置如vollrath混合器将PU泡沫的起始物质混合。
3D间隔织物和PU泡沫的混合起始物质的投料顺序并不重要。实际上,可先将织物加入模具中,然后加入PU泡沫的起始物质;或者可首先将PU泡沫的起始物质加入模具中,然后加入织物;或者可将织物粘贴到模具的(上和下)内表面上,然后加入PU泡沫的起始物质。
特别地,3D间隔织物增强的PU复合材料通过将用于制备PU泡沫的反应混合物混合,然后将混合物注入3D间隔织物中形成。更特别地,第一步是将用于制备PU泡沫的所有组分均匀混合在一起。随后,将混合物注入已经放置有3D间隔织物的模具中。注入可通过使用真空辅助树脂传递模塑(VARTM)或通过直接浇铸来进行。就此而言,令人惊讶地发现,通过使用本发明的特定PU泡沫配方,可将用于形成PU泡沫的原料直接(即不使用任何辅助设备如真空辅助注入设备)注入其中已经放置有3D间隔织物的模具中。这使得注入变得更容易,且降低了生产成本。
注入可以以使得用于制备PU泡沫的反应混合物沿间隔纱线方向流过3D间隔织物的方式进行。在制备过程中,可加热模具的顶部和底部表面,例如借助电或水浴加热系统。注入期间的温度为约20-约50℃。在形成复合材料的同时,PU发泡。在注入后,将温度保持一定时间,例如约5-约30分钟,以继续发泡。在发泡后,将复合材料从模具中取出并静置一段时间,例如约8-约32小时,优选约10-约24小时,直至复合材料稳定。
已发现本发明的复合材料具有改善的机械性能和独特的性能,例如独特的各向异性效应。对于鞋材,特别是鞋底而言,通常需要在对应于脚弓的部分容易上下弯曲,而在水平面内不易变形。因此,本发明复合材料的独特各向异性效应使得其非常适合用于鞋材,尤其是鞋底。而且,本发明复合材料的改善的机械性能使得得到的鞋材,特别是鞋底具有高机械性能。
因此,在另一方面,本发明涉及本发明的3D间隔织物增强的PU复合材料在鞋材中,特别是在鞋底中的用途。
在另一方面,本发明涉及一种鞋材,特别是鞋底,其包括本发明的3D间隔织物增强的PU复合材料。
在制备鞋底时,将3D织物以如下方式放入模具中的PU泡沫原料中:使得间隔纱线的方向构成所得鞋底的厚度方向,而织物的顶层和底层平行于所得鞋底的顶部和底部。在这种情况下,当步行或跑步时,鞋底会上下弯曲,即沿垂直于间隔纱线的方向弯曲,而在另外两个方向上,鞋底不容易变形。
本发明的其他实施方案描述在权利要求书、说明书和实施例中。不言而喻,上文提及的特征和下文将要解释的特征不仅可以以在每种情况下指出的组合形式使用,而且可以以其他组合形式使用,而不超出本发明的范围。
以下实施例说明了本发明的优点。
实施例
1.测量方法
在实验期间,测量了3D织物增强的PU复合材料的韧性、密度、硬度和机械性能。
3D织物增强的PU复合材料的密度通过使用DPX300LTE密度分析仪从顶层到底层测量。根据测试标准,应制备尺寸为5cm(长)×5cm(宽)×1cm(厚)的样品,然后放入室中并通过X射线进行扫描。因此,获得密度分布图。
3D织物增强的PU复合材料的硬度根据ASTMD 2240的测试标准通过使用获自KOBUNSHI KEIKI Co,Ltd的Asker C硬度计在间隔纱线的方向上测量。
3D织物增强的PU复合材料的拉伸强度根据DIN 53504的测试标准通过使用获自Zwick Roell Instrument&Technology Co,Ltd的Zwick/Roell测试机在间隔纱线的方向上测量。
3D织物增强的PU复合材料的撕裂强度根据DIN ISO 34-1方法A的测试标准通过使用获自Zwick Roell Instrument&Technology Co,Ltd的Zwick/Roell测试机在间隔纱线的方向上测量。
3D织物增强的PU复合材料的伸长率根据DIN 53504的测试标准通过使用获自Zwick Roell Instrument&Technology Co,Ltd的Zwick/Roell测试机在垂直于间隔纱线的方向上测量。
韧性通过用手弯曲3D织物增强的PU复合材料来测量。如果测试板可在垂直于间隔纱线的方向上弯曲超过30°,则韧性好;如果测试板不能弯曲超过30°,则韧性差。
对于聚酯配方,还进行水解测试。3D织物增强的PU复合材料的水解测试根据DINEN ISO 20344的测试标准测量。
2.制备复合材料的程序
通过混合相应的组分来分别制备表1和2中所示的A组分(对于运动鞋(sports)体系,将A组分保持在35℃下;对于便鞋(chappal)体系,将A组分保持在室温,20℃下)和B组分。同时,将模具的温度保持在25-50℃下(对于运动鞋体系,模具温度为23℃;对于便鞋体系,模具温度为50℃)。然后将65克A组分和45克B组分放入一个塑料杯中,用混合机(型号EWTHV 0.5,vollrath混合器)混合7-8秒。将62克A和B组分的混合物放入模具中。然后,将东华大学(Donghua University)所提供的PET制成的3D织物以织物的顶层和底层平行于模具的底部且织物置于模具中心的方式放入混合物中。然后闭合模具。5分钟后,打开模具并取出样品,在室温下保持24小时以进行固化。
表1基础配方(基于便鞋)
表2基础配方(运动鞋配方)
根据上述标准在获得的板上进行测试以测定密度、硬度、拉伸强度、伸长率及撕裂强度。对于聚酯体系,也测量了水解之前及之后的机械性能。结果分别显示于表3及4中。
表3基于便鞋配方(聚酯体系)的板的性能
表4基于运动鞋配方(聚醚体系)的板的性能
从表3及表4可以看出,用该3D织物增强后,所得板的拉伸强度及撕裂强度大幅增加。
由所述配方获得的测试板可在垂直于间隔纱线的方向上弯曲超过30°,而在与其垂直的另外两个方向上几乎不弯曲。
该复合材料的改善的机械性能可延长鞋底寿命,且该各向异性有助于使脚踝在行走或跑步时保持稳定与舒适。此外,该复合材料的外观也允许自由设计鞋子。
Claims (13)
1.一种3D间隔织物增强的PU复合材料,其由通过3D间隔织物增强的聚氨酯(PU)泡沫制成,其中所述聚氨酯通过使如下组分反应而制备:
(a)二异氰酸酯或多异氰酸酯,
(b)聚醚多元醇或聚酯多元醇,和
(c)任选的发泡剂。
2.如权利要求1所述的复合材料,其中所述聚醚多元醇或聚酯多元醇的官能度为约1.7-约2.5,优选为约1.8-约2.4,更优选为约1.8-约2.3。
3.如权利要求1或2所述的复合材料,其中所述聚醚多元醇或聚酯多元醇的羟值为约50-约270mg KOH/g,优选为约55-约200mg KOH/g,更优选为约55-约150mg KOH/g,甚至更优选为约55-约100mg KOH/g,最优选为约55-约80mg KOH/g。
4.如权利要求1-3中任一项所述的复合材料,其中所述聚醚多元醇或聚酯多元醇的分子量为约500-约6000,优选为约600-约4000,更优选为约1000-约2500。
5.如权利要求1-4中任一项所述的复合材料,其中所述聚醚多元醇或聚酯多元醇的多分散指数为约0.8-约1.3,优选为约0.9-约1.2,更优选为约0.95-约1.1。
6.如权利要求1-5中任一项所述的复合材料,其中所述织物由聚对苯二甲酸乙二醇酯(PET)、聚对苯二甲酸丁二醇酯(PBT)、尼龙或聚丙烯腈,更优选PET及PBT,最优选PET制成。
7.如权利要求1-6中任一项所述的复合材料,其中所述3D间隔织物的厚度为约2-约15mm,优选为约3-约12mm,更优选为约5-约10mm,最优选为约5.5-约8mm。
8.一种制备如权利要求1-7中任一项所述的复合材料的方法,其包括将3D间隔织物和PU泡沫的起始物质加入模具中,然后发泡。
9.如权利要求8所述的方法,其包括将用于制备PU泡沫的反应混合物混合,然后将混合物注入已放入模具中的3D间隔织物中。
10.如权利要求9所述的方法,其中注入通过使用真空辅助树脂传递模塑(VARTM)或通过直接浇铸,优选通过直接浇铸来进行。
11.如权利要求9或10所述的方法,其中注入以使得反应混合物沿间隔纱线方向流过3D间隔织物的方式进行。
12.如权利要求1-7中任一项所述的复合材料在鞋材,特别是在鞋底中的用途。
13.一种鞋材,特别是鞋底,其包含如权利要求1-7中任一项所述的复合材料。
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