CN113227299A - 热塑性聚氨酯热熔性粘合剂及其用途 - Google Patents

热塑性聚氨酯热熔性粘合剂及其用途 Download PDF

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CN113227299A
CN113227299A CN201980085551.3A CN201980085551A CN113227299A CN 113227299 A CN113227299 A CN 113227299A CN 201980085551 A CN201980085551 A CN 201980085551A CN 113227299 A CN113227299 A CN 113227299A
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thermoplastic polyurethane
melt adhesive
hot melt
polyurethane hot
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陈伯涵
周政宏
王江伟
范艳斌
芮祥鹏
吴建辉
黄昱霖
曾沛瑄
黄赐源
林彦文
张建丰
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Abstract

本发明涉及一种热塑性聚氨酯热熔性粘合剂，包含(a)异氰酸酯；(b)基于该多元醇的总重量包含至少5重量％聚烯烃多元醇的多元醇和(c)扩链剂的反应产物，其中该聚烯烃多元醇包含烯属不饱和基团。本发明还涉及一种使用该热塑性聚氨酯热熔性粘合剂制备鞋底组合体的方法和该热塑性聚氨酯热熔性粘合剂在制备该鞋底组合体重的用途。

Description

热塑性聚氨酯热熔性粘合剂及其用途
技术领域
本发明涉及一种可以用来制备鞋底组合体的热塑性聚氨酯热熔性粘合剂(用于粘合鞋外底和鞋内底)以及一种制备该鞋底组合体的方法。
技术背景
2013年品牌运动鞋的全球销量大约为US$465亿(来源：Sporting GoodsIntelligence)。大多数鞋底组合体通过粘合橡胶外底和乙烯-乙酸乙烯酯(EVA)发泡内底而得到。在现有制造方法中，不管是橡胶外底还是EVA发泡内底，需要分开施用不同的溶剂基底漆并在烘箱中除去该溶剂，然后分开涂敷溶剂基(或水基)聚氨酯(PU)胶并在烘箱中除去该溶剂(或水)，可以粘合该鞋外底和该鞋内底，直到完全除去该溶剂(或水)。上述操作费时费力，但还要求使用对人体和环境有害的有机溶剂。在环境保护意识高且政府法规日趋严格的现有情况下，制造商全部致力于避免使用有机溶剂，以实现更好的工作条件、绿色和环境友好的制造。
CN103756576B公开了一种用于粘合鞋底的热熔性粘合剂薄膜，其特征在于它按重量份包含下列原料：50-60份乙烯-乙酸乙烯酯(EVA)；30-60份改性乙烯-丙烯酸乙酯(EEA)；15-35份苯乙烯-丁二烯嵌段共聚物；5-20份萜烯树脂或石油树脂；和0.1-0.5份二(叔丁基过氧异丙基)苯，用于粘合鞋外底和内底。
CN104559843A公开了一种用于粘合橡胶/发泡EVA复合鞋底的热熔性粘合剂薄膜，包含热熔性粘合剂薄膜和隔离薄膜，其特征在于该热熔性粘合剂薄膜通过按重量份的下列原料制备：60-95份聚乙烯-酯共聚物；5-40份橡胶；和0.1-8份辅助剂。在该使用方法中，将该热熔性粘合剂薄膜粘贴于该橡胶外底表面并与该橡胶外底一起硫化，然后将该硫化的橡胶外底与该EVA内底组合，这可以将该热熔性粘合剂薄膜与该橡胶外底和该内底完全粘合在一起并且不会在该硫化工艺过程中产生气泡，从而提高了其粘合强度。
热塑性聚氨酯(TPU)由于其良好的弹性体性能和熔融加工性能而具有重要的工业应用。有关TPU的生产、性能和应用的综述例如在Kunststoff Handbuch[G.Becker，D.Braun]，第7卷，“Polyurethanes”，Munich，Vienna，Carl Hanser Verlag，1983中给出。TPU通常由线性多元醇如聚酯二醇、聚醚二醇或聚碳酸酯二醇，有机二异氰酸酯和通常为短链的二官能醇(即扩链剂)合成。TPU可以通过连续方法或不连续方法生产。众所周知的方法例如是GB-A1 057 018中公开的带式法和DE-A19 64 834中公开的挤出机法。可熔融加工的聚氨酯弹性体的合成可以逐步进行(即预聚物方法)或者通过所有组分在一个反应阶段中的同时反应(一步法)进行。
热塑性聚氨酯热熔性粘合剂(TPU HMA)通常极具极性，因此对于也为极性的材料(如天然皮革、聚酯织物、聚酰胺织物)而言，存在非常好的粘附。然而，当TPU HMA遭遇非常低极性(或非极性)材料如玻璃、橡胶、EVA和聚烯烃时，可能发生不良粘附。由于该原因，通常使用特殊材料来改性TPU HMA以改善其对低极性(非极性)材料的粘附。US 4,718,956公开了适合将TPU暂时粘合于玻璃的十八烷基三乙氧基硅烷。WO2004/054113公开了使用可以掺入TPU中的二官能硅烷。硅烷也可以接枝到TPU上，例如如WO 00/75213或S.Dassin等，Polymer Eng.Sci.，2002，42(8)，1724-1739所公开的那样。然而，尽管上述改性TPU HMA在对玻璃的粘附上具有显著改进，但它仍然在对橡胶和EVA的粘附上没有显著改进。
CN101611086B公开了一种组合物，包含A)至少一种烯烃基聚合物或至少一种卤代乙烯基聚合物或至少一种弹性体橡胶；B)至少一种热塑性聚氨酯；和C)至少一种聚二烯-或聚二醇基聚氨酯，以及一种包含至少一种由该发明组合物形成的组件的鞋类制品。CN101616983B还公开了一种包含至少一种由np-PO和聚二烯基聚氨酯或聚二醇基聚氨酯的共混物形成的组件的鞋类制品。该鞋类制品选自鞋外底、鞋内底、鞋大底、包塑制品、天然皮革制品、合成皮革制品、鞋帮、层压制品、涂敷制品、靴子、凉鞋、套鞋、塑料鞋及其组合。
US 6,323,299 B1公开了一种制备热塑性聚氨酯弹性体组合物的方法，包括：(a)首先使该聚二烯和该异氰酸酯在70-100℃下反应10-60分钟，(b)向(a)的反应产物中加入该聚合二醇并使这些组分在70-100℃下反应60-150分钟而形成预聚物，以及(c)加入该扩链剂并使这些组分在70-125℃下反应1-24小时而形成呈现出柔软度和高强度的热塑性聚氨酯。
然而，仍然需要找到一种热熔性粘合剂，其对低极性(非极性)材料，尤其是橡胶鞋外底和EVA鞋内底具有良好粘附，环境友好并且易于在更好的工作条件下使用。
发明概述
为此，本发明提供了一种热塑性聚氨酯热熔性粘合剂，包含(a)异氰酸酯；(b)基于该多元醇的总重量包含至少5重量％聚烯烃多元醇的多元醇和(c)扩链剂的反应产物，其中该聚烯烃多元醇包含烯属不饱和基团。
上述热塑性聚氨酯热熔性粘合剂具有的流动开始温度(Tfb)通过使用ShimadzuFlowtester Capillary Rheometer CFT-500D由JIS K7311-1995(模头：(a))测量为至少70℃，优选至少75℃，更优选至少80℃，以避免该鞋外底/内底层压体在集装箱中运输的过程中脱层。
本发明还提供了一种生产鞋底组合体的方法，包括(1)将该热塑性聚氨酯热熔性粘合剂的薄片或粉末放置在该鞋外底上，加热硫化；以及(2)将鞋内底放置在该热塑性聚氨酯热熔性粘合剂上而得到鞋底预制件，加热并压制(即二次压制鞋底模具)该鞋底预制件而生产该鞋底组合体。上述热塑性聚氨酯热熔性粘合剂对低极性(或非极性)材料，尤其是橡胶外底和EVA内底具有良好的粘附并且环境友好和易于使用。
附图说明
图1是根据传统方法生产鞋底组合体的工艺流程图。
图2是根据本发明的一个实施方案生产鞋底组合体的工艺流程图。
实施方案
在本发明的一个实施方案中，该热塑性聚氨酯热熔性粘合剂包含(a)异氰酸酯；(b)基于该多元醇的总重量包含至少5重量％，优选至少10重量％，更优选至少15重量％聚烯烃多元醇的多元醇和(c)扩链剂的反应产物，其中该聚烯烃多元醇包含烯属不饱和基团。
根据本发明，合适的异氰酸酯如Justus Liebigs Annalen der Chemie，562，第75-136页所述例如可以包括芳族、脂族、脂环族、芳脂族、杂环异氰酸酯。优选该异氰酸酯可以包括芳族异氰酸酯、脂族异氰酸酯、脂环族异氰酸酯或其组合。
优选该芳族异氰酸酯是一种芳族二异氰酸酯并且例如可以包括2,4-甲苯二异氰酸酯、2,6-甲苯二异氰酸酯、4,4'-二苯基甲烷二异氰酸酯、2,4-二苯基甲烷二异氰酸酯、2,2'-二苯基甲烷二异氰酸酯、尿烷改性的液体4,4'-二苯基甲烷二异氰酸酯和/或2,4-二苯基甲烷二异氰酸酯、4,4'-二异氰酸酯基-1,2-二苯基乙烷、1,5-萘二异氰酸酯及其组合。
在优选实施方案中，合适的芳族二异氰酸酯例如可以包括2,4-和2,6-甲苯二异氰酸酯、2,4-和2,6-甲苯二异氰酸酯的混合物、4,4'-二苯基甲烷二异氰酸酯、2,4-二苯基甲烷二异氰酸酯和2,2'-二苯基甲烷二异氰酸酯、2,4-二苯基甲烷二异氰酸酯和4,4'-二苯基甲烷二异氰酸酯的混合物、尿烷改性的液体4,4'-二苯基甲烷二异氰酸酯和/或2,4-二苯基甲烷二异氰酸酯、4,4'-二异氰酸酯基-1,2-二苯基乙烷和1,5-萘二异氰酸酯。
优选该脂族异氰酸酯是一种脂族二异氰酸酯并且可以包括亚乙基二异氰酸酯、1,4-四亚甲基二异氰酸酯、1,12-十二烷二异氰酸酯、1,6-六亚甲基二异氰酸酯及其组合。
优选该脂环族异氰酸酯是一种脂环族二异氰酸酯并且可以包括异佛尔酮二异氰酸酯、1,4-环己烷二异氰酸酯、1-甲基-2,4-环己烷二异氰酸酯、1-甲基-2,6-环己烷二异氰酸酯及其相应异构体混合物，4,4'-、2,4-和2,2'-二环己基甲烷二异氰酸酯及其相应异构体混合物及其组合。
根据本发明，优选使用芳族和/或脂环族二异氰酸酯。更具体而言，特别优选4,4'-二苯基甲烷二异氰酸酯、1,4-环己烷二异氰酸酯、1,6-六亚甲基二异氰酸酯、异佛尔酮二异氰酸酯和二环己基甲烷二异氰酸酯。这些二异氰酸酯可以单独或者作为混合物使用。它们还可以与至多15mol％(相对于二异氰酸酯的总量计算)多异氰酸酯使用。然而，多异氰酸酯的最大加入量应使所得产物仍可熔融加工。
组分(b)中的该聚烯烃多元醇或其他多元醇优选具有450-9,900g/mol，更优选600-8,000g/mol，进一步优选800-6,000g/mol的数均分子量(Mn)并且优选平均具有1.5-3.0个，更优选1.8-2.5个羟基官能基团。
本发明中的聚烯烃多元醇可以是含有聚烯烃链段的多元醇。聚烯烃链段可以由多烯属不饱和单体得到。
优选该多烯属不饱和单体是二烯属或三烯属不饱和单体。优选该多烯属不饱和单体是烃基取代的多烯属不饱和单体，更优选共轭二烯单体。烃基可以包括线性烷基和/或环烷基。共轭二烯单体优选含有4-10个碳原子，优选4-6个碳原子。在一个实施方案中，该共轭二烯单体是丁二烯、异戊二烯或其组合。
在优选实施方案中，该聚烯烃多元醇是聚二烯多元醇，更优选聚丁二烯二醇、聚异戊二烯二醇或其组合。
在优选实施方案中，该多元醇基于该多元醇的总重量可以包含5-90重量％，优选8-60重量％，更优选10-50重量％，甚至更优选10-40重量％，仍甚至更优选5-20重量％，更优选10-15重量％该聚烯烃多元醇。
在一个实施方案中，该多元醇可以进一步包含聚酯多元醇、聚醚多元醇、聚碳酸酯多元醇或其组合。
合适的聚酯多元醇包括例如由具有2-12个碳原子，优选4-6个碳原子的二羧酸和多元醇得到的那些。合适的二羧酸例如包括下列化合物：脂族二羧酸，如琥珀酸、戊二酸、己二酸、辛二酸、壬二酸和癸二酸；或芳族二羧酸，如邻苯二甲酸、间苯二甲酸和对苯二甲酸。二羧酸可以单独或者作为混合物使用，例如作为琥珀酸、戊二酸和己二酸的混合物使用。为了制备聚酯多元醇，可以任选使用相应二羧酸衍生物，如在醇残基中具有1-4个碳原子的羧酸二酯、酸酐或酰氯代替二羧酸。合适多元醇的实例包括具有2-10个碳原子，优选2-6个碳原子的二醇，如乙二醇、二甘醇、1,4-丁二醇、1,5-戊二醇、1,6-己二醇、1,10-癸二醇、2,2-二甲基-1,3-丙二醇、1,3-丙二醇或二丙二醇。取决于所需性能，该多元醇可以单独或者作为混合物使用。优选的聚酯多元醇包括聚(乙二醇己二酸酯)、聚(1,4-丁二醇己二酸酯)、聚(乙二醇/1,4-丁二醇己二酸酯)、聚(1,6-己二醇/新戊二醇己二酸酯)、聚(1,6-己二醇/1,4-丁二醇己二酸酯)和聚己内酯，ω-羟基羧酸如ω-羟基己酸的缩合产物或者内酯如任选取代的ω-己内酯的聚合产物。碳酸与上述二醇，尤其是具有4-6个碳原子的那些如1,4-丁二醇或1,6-己二醇的酯也合适。优选该聚酯多元醇具有450-9,900g/mol的数均分子量(Mn)并且可以单独或作为混合物使用。
合适的聚醚多元醇可以按如下制备：例如使一种或多种具有2-4个碳原子的氧化烯和具有两个或更多个活性氢原子的起始剂分子反应。作为举例可以提到的氧化烯包括氧化乙烯、1,2-氧化丙烯、表氯醇、1,2-氧化丁烯和2,3-氧化丁烯。优选使用氧化乙烯、氧化丙烯以及1,2-氧化丙烯和氧化乙烯的混合物。该氧化烯可以单独使用，或者依次使用，或者以混合物的形式使用。合适的起始剂分子例如包括下列化合物：水；胺醇，如N-烷基二乙醇胺，如N-甲基二乙醇胺；以及二醇，如乙二醇、1,3-丙二醇、1,4-丁二醇和1,6-己二醇。任选还可以使用起始剂分子的混合物。合适的聚醚多元醇还包括四氢呋喃的含羟基聚合产物。基于二官能聚醚多元醇的重量百分数，还可以使用比例为约0-30重量％的三官能聚醚多元醇。三官能聚醚多元醇的最大量应使所得最终产物仍可熔融加工。优选该聚醚多元醇具有600-5,000g/mol的数均分子量(Mn)。这些聚醚多元醇可以单独或者作为混合物使用。
根据本发明，该扩链剂是二醇基扩链剂，如含有2-14个碳原子的二醇化合物，包括乙二醇、1,2-丙二醇、1,3-丙二醇、1,3-丁二醇、1,4-丁二醇、2,3-丁二醇、1,5-戊二醇、1,2-己二醇、1,6-己二醇、二甘醇、二丙二醇、1,4-环己二醇、1,4-二甲醇环己烷和新戊二醇。优选用作扩链剂的化合物是乙二醇、1,4-丁二醇、1,6-己二醇、1,4-二(β-羟基乙基)氢醌或1,4-二(β-羟基乙基)双酚A。还可以使用较少量的三醇。在优选实施方案中，扩链剂包括乙二醇、丙二醇、1,4-丁二醇、1,5-戊二醇、1,6-己二醇、氢醌二(2-羟基乙基)醚及其组合。更优选该扩链剂是1,4-丁二醇。
在优选实施方案中，该热塑性聚氨酯热熔性粘合剂包含(a)4-40重量％该异氰酸酯；(b)50-95重量％该多元醇和(c)1-10重量％该扩链剂的反应产物，所述重量百分数基于(a)、(b)和(c)的总重量。
该热塑性聚氨酯热熔性粘合剂基于该热塑性聚氨酯热熔性粘合剂的重量包含90-100重量％，优选95-100重量％上述反应产物。
本发明的TPU HMA还可以含有至多约10重量％一种或多种常用辅助剂和添加剂。典型的辅助剂和添加剂包括但不限于催化剂、滑爽剂和隔离剂如脂肪酸酯及其金属皂、脂肪酸酰胺、脂肪酸酯酰胺和聚硅氧烷化合物，光稳定剂、增塑剂、抗粘连剂、抑制剂、抗水解剂、热和衰退稳定剂、染料、颜料、无机和/或有机填料、具有抑制霉菌和细菌的活性物质的填料及其混合物。有关上述辅助剂和添加剂的进一步详情可以在文献中找到。具体而言，这些详情例如被分别在1962年和1964年出版的J.H.Saunders和K.C.Frisch，“HighPolymers”，XVI卷，“聚氨酯”，部分I和II，Verlag Interscience Press或R.Gchter和H.Mller(Hanser Verlag Munich 1990)，“Taschenbuch fr Kunststoff-Additive”或者DE-A29 01 774公开。光稳定剂优选是UV稳定剂、抗氧化剂和/或HALS(受阻胺光稳定剂)化合物。有关合适光稳定剂的进一步详情可以在文献中，例如在H.Zweifel，“PlasticsAdditives Handbook”，2001，第5版，Carl Hanser Verlag，Munich中找到。
本发明的热塑性聚氨酯热熔性粘合剂通过一步法制备，即热塑性聚氨酯热熔性粘合剂通过使所有组分同时反应而制备。
根据本发明，提供了一种生产鞋底组合体的方法，包括：(1)将热塑性聚氨酯热熔性粘合剂的薄片或粉末放置在该鞋外底上，加热硫化；以及(2)将鞋内底放置在该热塑性聚氨酯热熔性粘合剂上而得到鞋底预制件，加热并压制(即二次压制鞋底模具)该鞋底预制件而生产该鞋底组合体。在(1)或(2)中的加热在常规温度下进行，例如加热在120-180℃，更优选140-180℃的温度下进行。
在本发明的一个实施方案中，该方法包括下列步骤：
(1)将该热塑性聚氨酯热熔性粘合剂的薄片或粉末以及然后是隔离薄膜放置在该鞋外底上；
(2)加热硫化；
(3)除去该隔离薄膜；
(4)脱模和去毛刺；
(5)将鞋内底放置在该热塑性聚氨酯热熔性粘合剂上而得到鞋底预制件，加热并压制(即二次压制鞋底模具)；以及
(6)脱模和去毛刺而得到该鞋底组合体。
图1说明根据传统方法生产鞋底组合体的工艺流程图，而图2说明根据本发明的一个实施方案生产鞋底组合体的工艺流程图。通过比较图1和图2发现该传统方法比本发明方法更复杂。具体而言，本发明方法省去了许多加工步骤，如加工鞋外底的粗加工、洗涤、干燥、涂敷橡胶底漆、二次干燥、胶合、三次干燥以及加工鞋内底的二次压制内底模具、粗加工、洗涤、干燥、涂敷EVA底漆、二次干燥、胶合、三次干燥。根据本发明方法通常需要约18-28分钟来完成鞋底组合体，而根据传统方法需要约46-75分钟来完成鞋底组合体。因此，本发明不仅节省了时间成本，而且节省了经济成本，并且避免了使用挥发性物质，这是环境友好的。
在一个实施方案中，该外底由橡胶、聚氯乙烯(PVC)、热塑性聚氨酯(TPU)、热塑性酯弹性体(TPEE)或其组合制成。更优选该外底由橡胶制成。
在一个实施方案中，该内底由乙烯/乙酸乙烯酯(EVA)泡沫、聚氯乙烯(PVC)泡沫、热塑性聚氨酯(TPU)泡沫、热塑性酯弹性体(TPEE)泡沫或其组合制成。更优选该内底由乙烯/乙酸乙烯酯(EVA)泡沫制成。
本发明还提供了一种鞋底组合体，包括上述热塑性聚氨酯热熔性粘合剂、鞋外底和鞋内底。
在一个实施方案中，在该鞋底组合体中鞋外底和鞋内底之间的剥离强度大于2.5kgf/cm，优选大于3.0kgf/cm，更优选大于4.0kgf/cm。
实施例
本发明参考下列实施例和附图说明，这些实施例和附图仅仅用于说明目的且不应解释为限制本发明范围。
原料及其在实施例和对比例中的用量列于表1中。
Krasol LBH-P 2000：Mn＝1,956～2,317，OH值＝46.0～54.5mg KOH/g，羟基官能基团＝1.9；
AC1530PH：Mn＝2,877～3,074，OH值＝36.5～39.0mg KOH/g，羟基官能基团＝2.0。
Figure BDA0003128036460000091
实施例1-5
在通过使用桨叶混合机(SHIN KWANG GR-150R)以500转/分钟(rpm)的转速搅拌1分钟下将各组分的混合物加热至80℃。然后将该TPU HMA出料。将该TPU HMA在100℃下后热处理60分钟，然后造粒。
对比例1
对比例1通过使用表1中的各组分由与实施例1-5相同的程序进行。
将在实施例1、2、3、4、5和对比例1中制备的TPU HMA加工成薄片并放置在橡胶外底和EVA发泡内底之间，通过在150～165℃下加热5分钟而活化该TPU HMA，在冷却之后得到鞋底成型制品。使该成型制品在室温下陈化至少24小时并用拉伸试验机(装置型号：GOTECHAI-7000-M)根据ASTM D1876测量该橡胶外底和该EVA发泡内底的剥离强度以及通过使用Shimadzu Flowtester Capillary Rheometer CFT-500D由JIS K7311-1995(模头：(a))测量Tfb。测试结果示于表2中。
表2.TPU HMA的剥离强度和Tfb比较
样品 聚烯烃多元醇含量(重量％) 剥离强度(kgf/cm) Tfb(℃)
实施例1 5％ 2.8 99.6℃
实施例2 10％ 3.6 105.3℃
实施例3 15％ 4.5 107.9℃
实施例4 15％ 4.4 104.2℃
实施例5 20％ 3.0 102.7℃
对比例1 0％ 0.8 106.5℃
表2表明对比例1的剥离强度是0.8kgf/cm，远低于市场上对剥离强度所要求的标准值2.5kgf/cm，而实施例1-5，尤其是实施例2-5的剥离强度超过标准值2.5kgf/cm。
在实施例3和4中，尽管其剥离强度相互接近，但实施例4由于加入催化剂而可以减少生产时间。此外，就抗水解性以及耐日光、UV光和热变黄而言实施例4借助抗水解剂、UV吸收剂、HALS和抗氧化剂的加入优于实施例3。
本领域技术人员明了的是在不背离本发明范围或要旨下可以对本发明作出各种改性和变化。因此，本发明意欲覆盖落入所附权利要求书范围内的该类改性和变化及其等价物。

Claims (25)

1.一种热塑性聚氨酯热熔性粘合剂，包含(a)异氰酸酯；(b)基于所述多元醇的总重量包含至少5重量％聚烯烃多元醇的多元醇和(c)扩链剂的反应产物，其中所述聚烯烃多元醇包含烯属不饱和基团。
2.根据权利要求1的热塑性聚氨酯热熔性粘合剂，其中所述聚烯烃多元醇是聚二烯多元醇。
3.根据权利要求2的热塑性聚氨酯热熔性粘合剂，其中所述聚二烯多元醇的二烯单体单元衍生于含有4-10个碳原子，优选4-6个碳原子的共轭二烯单体。
4.根据权利要求1-3中任一项的热塑性聚氨酯热熔性粘合剂，其中所述多元醇具有450-9,900g/mol，优选600-8,000g/mol，更优选800-6,000g/mol的数均分子量(Mn)并且平均具有1.5-3.0个，优选1.8-2.5个羟基官能基团。
5.根据权利要求1-3中任一项的热塑性聚氨酯热熔性粘合剂，其中所述多元醇包含至少5重量％，优选至少10重量％，更优选至少15重量％所述聚烯烃多元醇。
6.根据权利要求1-3中任一项的热塑性聚氨酯热熔性粘合剂，其中所述多元醇包含5-90重量％，优选8-60重量％，更优选10-50重量％，甚至更优选10-40重量％，仍甚至更优选5-20重量％，仍甚至更优选10-15重量％所述聚烯烃多元醇。
7.根据权利要求2或3的热塑性聚氨酯热熔性粘合剂，其中所述聚二烯多元醇是聚丁二烯二醇、聚异戊二烯二醇或其组合。
8.根据权利要求1-3中任一项的热塑性聚氨酯热熔性粘合剂，其中所述热塑性聚氨酯热熔性粘合剂具有至少70℃，优选至少75℃，更优选至少80℃的流动开始温度(Tfb)。
9.根据权利要求1-3中任一项的热塑性聚氨酯热熔性粘合剂，其中所述多元醇进一步包含聚酯多元醇、聚醚多元醇、聚碳酸酯多元醇或其组合。
10.根据权利要求1-3中任一项的热塑性聚氨酯热熔性粘合剂，其中所述异氰酸酯包括芳族异氰酸酯、脂族异氰酸酯、脂环族异氰酸酯及其组合。
11.根据权利要求10的热塑性聚氨酯热熔性粘合剂，其中所述芳族异氰酸酯是芳族二异氰酸酯，包括2,4-甲苯二异氰酸酯、2,6-甲苯二异氰酸酯、4,4'-二苯基甲烷二异氰酸酯、2,4-二苯基甲烷二异氰酸酯、2,2'-二苯基甲烷二异氰酸酯、尿烷改性的液体4,4'-二苯基甲烷二异氰酸酯和/或2,4-二苯基甲烷二异氰酸酯、4,4′-二异氰酸酯基-1,2-二苯基乙烷、1,5-萘二异氰酸酯及其组合。
12.根据权利要求10的热塑性聚氨酯热熔性粘合剂，其中所述脂族异氰酸酯是脂族二异氰酸酯，包括亚乙基二异氰酸酯、1,4-四亚甲基二异氰酸酯、1,12-十二烷二异氰酸酯、1,6-六亚甲基二异氰酸酯及其组合。
13.根据权利要求10的热塑性聚氨酯热熔性粘合剂，其中所述脂环族异氰酸酯是脂环族二异氰酸酯，包括异佛尔酮二异氰酸酯，1,4-环己烷二异氰酸酯，1-甲基-2,4-环己烷二异氰酸酯，1-甲基-2,6-环己烷二异氰酸酯及其相应异构体混合物，4,4'-、2,4-和2,2'-二环己基甲烷二异氰酸酯及其相应异构体混合物及其组合。
14.根据权利要求1-3中任一项的热塑性聚氨酯热熔性粘合剂，其中所述扩链剂是二醇基扩链剂，包括乙二醇、丙二醇、1,4-丁二醇、1,5-戊二醇、1,6-己二醇、氢醌二(2-羟基乙基)醚及其组合。
15.根据权利要求14的热塑性聚氨酯热熔性粘合剂，其中所述扩链剂是1,4-丁二醇。
16.根据权利要求1-3中任一项的热塑性聚氨酯热熔性粘合剂，包含(a)4-40重量％异氰酸酯；(b)50-95重量％多元醇和(c)1-10重量％扩链剂的反应产物，所述重量百分数基于(a)、(b)和(c)的总重量。
17.根据权利要求1-3中任一项的热塑性聚氨酯热熔性粘合剂，其中所述热塑性聚氨酯热熔性粘合剂基于所述热塑性聚氨酯热熔性粘合剂的重量含有90-100重量％所述反应产物。
18.根据权利要求1-3中任一项的热塑性聚氨酯热熔性粘合剂，进一步包含一种或多种选自催化剂、滑爽剂和隔离剂、光稳定剂、增塑剂、抗粘连剂、抑制剂、抗水解剂、热和衰退稳定剂、染料、颜料、无机和/或有机填料、具有抑制霉菌和细菌的活性物质的填料及其混合物的添加剂。
19.根据权利要求1-3中任一项的热塑性聚氨酯热熔性粘合剂，其中所述热塑性聚氨酯热熔性粘合剂通过一步法制备。
20.一种生产鞋底组合体的方法，包括(1)将根据权利要求1-19中任一项的热塑性聚氨酯热熔性粘合剂的薄片或粉末放置在所述鞋外底上，加热硫化；以及(2)将鞋内底放置在所述热塑性聚氨酯热熔性粘合剂上而得到鞋底预制件，加热并压制所述鞋底预制件而生产所述鞋底组合体。
21.根据权利要求20的方法，包括下列步骤：
(1)将所述热塑性聚氨酯热熔性粘合剂的薄片或粉末以及然后是隔离薄膜放置在所述鞋外底上；
(2)加热硫化；
(3)除去所述隔离薄膜；
(4)脱模和去毛刺；
(5)将鞋内底放置在所述热塑性聚氨酯热熔性粘合剂上而得到鞋底预制件，加热并压制；以及
(6)脱模和去毛刺而得到所述鞋底组合体。
22.根据权利要求20或21的方法，其中所述鞋外底由橡胶、聚氯乙烯(PVC)、热塑性聚氨酯(TPU)、热塑性酯弹性体(TPEE)或其组合制成。
23.根据权利要求20或21的方法，其中所述鞋内底由乙烯/乙酸乙烯酯(EVA)泡沫、聚氯乙烯(PVC)泡沫、热塑性聚氨酯(TPU)泡沫、热塑性酯弹性体(TPEE)或其组合制成。
24.一种鞋底组合体，包括根据权利要求1-19中任一项的热塑性聚氨酯热熔性粘合剂、鞋外底和鞋内底。
25.根据权利要求24的鞋底组合体，其中所述鞋底组合体中所述鞋外底和所述鞋内底之间的剥离强度大于2.5kgf/cm，优选大于3.0kgf/cm，更优选大于4.0kgf/cm。
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