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CN113631616A - 水性聚氨酯分散体及其制备方法 - Google Patents

水性聚氨酯分散体及其制备方法 Download PDF

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Publication number
CN113631616A
CN113631616A CN201980094600.XA CN201980094600A CN113631616A CN 113631616 A CN113631616 A CN 113631616A CN 201980094600 A CN201980094600 A CN 201980094600A CN 113631616 A CN113631616 A CN 113631616A
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Prior art keywords
isocyanate
groups
aqueous polyurethane
polyurethane dispersion
component
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CN113631616B (zh
Inventor
胡小链
张朝
邰向阳
冯艳丽
马标
凌玲
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Dow Global Technologies LLC
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Dow Global Technologies LLC
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Abstract

提供了一种水性聚氨酯分散体。所述水性聚氨酯分散体通过使用三官能聚醚多元醇作为用于形成预聚物的多元醇的一部分以及使用亲水性氨基硅氧烷助扩链剂来制备，并且可以表现出优异的性能特性，诸如增强的色牢度、改善的低温稳定性、良好的抗粘性、巴利耐弯曲性、耐磨性和机械性质。还提供了一种用所述水性聚氨酯分散体制备的层压合成皮革制品以及用于制备所述合成皮革制品的方法。

Description

水性聚氨酯分散体及其制备方法
技术领域
本公开涉及一种水性聚氨酯分散体及其制备方法、一种包含衍生自所述水性聚氨酯分散体的皮膜的层压合成皮革制品及其制备方法。用所述水性聚氨酯分散体制备的层压合成革制品表现出优异的性能特性的组合，所述优异的性能特性诸如增强的色牢度、改善的低温稳定性、良好的抗粘性、巴利耐弯曲性(bally flex resistance)、耐磨性和机械性质。
背景技术
合成皮革在人们的日常生活中得到了广泛的应用，从衣服、鞋类、袋子和行李箱、家庭装饰品到汽车座椅。合成皮革提供了与天然皮革类似的性能和手感，具有更好的成本优势。合成皮革是通过将聚合物涂覆在织物基材上或将聚合物浸渍到织物基材中制造而成，并且最常用的聚合物是聚氨酯。传统工艺是用聚氨酯树脂在挥发性有机溶剂(诸如二甲基甲酰胺(DMF)、甲基乙基酮(MEK)和甲苯)中的溶液进行的。PU的多孔结构是通过将经涂覆的或经浸渍的织物基材引入到水浴中，以受控的方式沉淀PU聚合物链产生的。这种多孔结构对合成皮革赋予与天然皮革类似的手感是非常关键且必不可少的。然而，挥发性有机溶剂对于工厂操作工、消费者和环境而言都是非常有害的。因此，合成皮革工业被推向无溶剂制造工艺，以使PU合成皮革制造中挥发性有机溶剂的使用最小化。由于越来越严格的环境法规，水性聚氨酯分散体(PUD)正在不断替代合成皮革行业中应用的常规溶剂型聚氨酯。目前，大多数水性PUD是基于聚酯多元醇和脂肪族异氰酸酯，因为它们具有良好的机械性质(诸如拉伸强度和模量)。然而，基于聚酯多元醇的PUD存在很多问题，例如，耐水解性差，成本高，以及由于聚酯预聚物的高粘度在水中的分散性低。基于聚醚多元醇的PUD没有这样的问题，但由于聚醚多元醇固有的柔软性，其机械性质和抗粘性能较差。一种新开发的用于生产合成皮革的技术是将衍生自聚氨酯分散体的外部乳化的皮层与非溶剂2K(即，双组分)PU泡沫层层压，但层压后的合成皮革的皮层表现出的抗粘性能较差，不能满足合成皮革应用的要求，如客户不可接受的皮膜中有任何轻微的粘性。此外，通过内部乳化生产的传统商业化的脂肪族PUD仍包含少量溶剂，并且与下层2K泡沫层的粘合性较差，因此必须在由PUD形成的表层与下层2K泡沫层之间设置粘合层。仍然需要开发一种技术，通过该技术可以在不使用中间粘合层的情况下制备由衍生自无溶剂外部乳化的PUD的表层和非溶剂2K PU泡沫层组成的合成皮革。此外，在用于制备合成皮革的表层时，PUD或PUD配制物应满足许多要求，包括特定的机械性质、抗粘性、巴利耐弯曲性、耐磨性、色牢度、高温/低温稳定性。
持续探索后，我们惊奇地发现通过使用至少一种三羟基聚醚多元醇作为用于形成预聚物的多元醇的一部分和亲水性氨基硅氧烷助扩链剂制备的PUD可以满足上述要求中的一个或多个。
发明内容
本公开提供了一种独特的水性聚氨酯分散体以及一种使用所述水性聚氨酯分散体制备的层压合成皮革制品。
在本公开的第一方面，本公开提供了一种水性聚氨酯分散体，所述水性聚氨酯分散体包含分散在水中的聚氨酯颗粒，其中所述水性聚氨酯分散体衍生自以下物质的反应：
(A)包含一种或多种具有至少两个异氰酸酯基团的化合物的异氰酸酯组分；
(B)包含一种或多种具有至少两个异氰酸酯反应性基团的化合物的异氰酸酯反应性组分，其中所述异氰酸酯反应性组分包含羟基官能度为3.0以及重均分子量为1,500至12,000g/mol的聚醚多元醇；
(C)由式I表示的亲水性氨基硅氧烷化合物：
Figure BDA0003275528990000021
其中每个R独立地表示甲基、乙基、正丙基、异丙基、正丁基、异丁基、仲丁基、叔丁基、正戊基、异戊基、叔戊基、新戊基、环己基、苯基、乙烯基、烯丙基或-(OCH2CH2)a-O-CH2-CH＝CH2；
R1是-(CH2)mNH2或-(CH2)s-NH-(CH2)tNH2；
R2是-CH2CH2CH2O(CH2CH2O)nH；并且
R3、R4、R5、R6和R7中的每一个独立地选自由甲基、乙基、正丙基、异丙基、正丁基、异丁基、仲丁基、叔丁基、正戊基、异戊基、叔戊基、新戊基、环己基和苯基组成的组；
其中a是1至10的整数；x是20至500的整数；y是1至10的整数；z是1至10的整数；m是1至5的整数；s是整数1、2、3、4或5；t是整数1、2、3、4或5；并且n是5至20的整数；
(D)催化剂；
(E)表面活性剂；
(F)扩链剂；以及
(G)水。
根据本公开的优选实施方案，水性聚氨酯分散体为外部乳化的聚氨酯，所述外部乳化的聚氨酯不包含与聚氨酯的主链共价附接的阳离子或阴离子亲水侧基或能够转化为与聚氨酯的主链共价附接的阳离子或阴离子亲水性侧基的基团。
根据本公开的优选实施方案，异氰酸酯反应性组分(B)包含羟基官能度为3.0以及重均分子量为1,500至12,000g/mol的聚醚多元醇作为必要组分，并且可以可选地包含除上述聚醚多元醇外，具有至少两个异氰酸酯反应性基团的其他化合物。
在本公开的第二方面，本公开提供了一种用于生产如第一方面所述的水性聚氨酯分散体的方法，所述方法包括：(i)在存在所述催化剂(D)的情况下使所述异氰酸酯组分(A)与所述异氰酸酯反应性组分(B)反应以形成预聚物，其中所述预聚物包含游离异氰酸酯基团和衍生自羟基官能度为3.0以及重均分子量为1,500至12,000g/mol的聚醚多元醇的残余部分；以及(ii)在存在所述表面活性剂(E)和水(G)的情况下使所述预聚物与所述亲水性氨基硅氧烷化合物(C)和所述扩链剂(F)反应以形成所述水性聚氨酯分散体。
在本公开的第三方面，本公开提供了一种合成皮革制品，所述合成皮革制品从上到下包含：
衍生自如第一方面所述的水性聚氨酯分散体的聚氨酯皮膜；
衍生自2K PU复合组合物的基层；以及
可选的背衬基材。
在本公开的第四方面，本公开提供了一种用于制备如第三方面所述的合成皮革制品的方法，所述方法包括：
a)提供如第一方面所述的水性聚氨酯分散体；
b)用所述水性聚氨酯分散体形成所述聚氨酯皮膜；
c)将所述2K PU复合组合物施加到所述聚氨酯皮膜的一侧上以形成所述基层；以及
d)可选地，将所述背衬基材施加到所述基层的与所述聚氨酯皮膜相对的一侧上。
应理解，前面的一般性描述和以下的详细描述都只是示例性和解释性的，并不是对如所要求保护的本发明的限制。
附图说明
图1是本文所述的合成皮革制品的一个实施方案的横截面的示意图。
具体实施方式
除非另外定义，否则本文所用的所有技术和科学术语具有与本发明所属领域中的普通技术人员通常所理解相同的含义。此外，本文所提及的所有公开案、专利申请、专利以及其他参考文献都是以引用的方式并入。
如本文中所公开的，术语“组合物”、“配制物”或“混合物”是指不同组分的物理掺合物，其是通过用物理手段简单地混合不同组分来获得的。
如本文中所公开的，“和/或”意指“以及，或作为替代方案”。除非另外指示，否则所有范围都包括端点。
异氰酸酯组分
在各种实施方案中，异氰酸酯组分(A)所具有的平均官能度为至少约2.0、优选地约2至10、更优选地约2至约8、并且最优选地约2至约6。在一些实施方案中，异氰酸酯组分包括包含至少两个异氰酸酯基团的聚异氰酸酯化合物。合适的聚异氰酸酯化合物包括具有两个或更多个异氰酸酯基团的芳香族、脂肪族、环脂族和芳脂族聚异氰酸酯。在优选的实施方案中，聚异氰酸酯组分包含选自由以下项组成的组的聚异氰酸酯化合物：包含至少两个异氰酸酯基团的C4-C12脂肪族聚异氰酸酯、包含至少两个异氰酸酯基团的C6-C15环脂族或芳香族聚异氰酸酯、包含至少两个异氰酸酯基团的C7-C15芳脂族聚异氰酸酯以及它们的组合。在另一个优选的实施方案中，合适的聚异氰酸酯化合物包括间苯二异氰酸酯、2,4-甲苯二异氰酸酯和/或2,6-甲苯二异氰酸酯(TDI)、二苯基甲烷二异氰酸酯(MDI)的各种异构体、碳化二亚胺改性的MDI产物、六亚甲基-1,6-二异氰酸酯、四亚甲基-1,4-二异氰酸酯、环己烷-1,4-二异氰酸酯、六氢甲苯二异氰酸酯、氢化MDI、萘基-1,5-二异氰酸酯、异佛尔酮二异氰酸酯(IPDI)或它们的混合物。
替代地或另外，聚异氰酸酯组分还可以包含异氰酸酯官能度在2至10、优选地2至8、更优选地2至6的范围内的异氰酸酯预聚物。异氰酸酯预聚物可以通过使上述单体异氰酸酯组分与选自由以下项组成的组的一种或多种异氰酸酯反应性化合物反应而获得：乙二醇、1,2-丙二醇、1,3-丙二醇、1,3-丁二醇、1,4-丁二醇、1,4-丁炔二醇、1,5-戊二醇、新戊二醇、双(羟甲基)环己烷(诸如1,4-双(羟甲基)环己烷)、2-甲基丙烷-1,3-二醇、甲基戊二醇，二甘醇、三甘醇、四甘醇、聚乙二醇、二丙二醇、聚丙二醇、二丁二醇、聚丁二醇和三羟基聚醚多元醇(诸如特别用于异氰酸酯反应性组分(B)的三羟基聚醚多元醇)。用作聚异氰酸酯组分的合适的预聚物为NCO基团含量为2至40重量百分比、更优选地4至30重量百分比的预聚物。优选地通过二异氰酸酯和/或聚异氰酸酯与包括较低分子量的二醇和三醇的材料的反应来制备这些预聚物。个别实例为含有氨基甲酸酯基团的芳香族聚异氰酸酯，优选地NCO含量为5至40重量百分比，更优选地20至35重量百分比，其通过二异氰酸酯和/或聚异氰酸酯与例如较低分子量的二醇、三醇、氧化烯二醇、二氧化烯二醇或分子量高达约800的聚氧化烯二醇的反应而获得。这些多元醇可以单独使用或呈二氧化烯二醇和/或聚氧化烯二醇的混合物形式使用。例如，可以使用二甘醇、二丙二醇、聚氧乙烯二醇、乙二醇、丙二醇、丁二醇、聚氧丙烯二醇和聚氧丙烯-聚氧乙烯二醇。也可以使用聚酯多元醇，以及烷烃二醇，诸如丁二醇。其他也有用的二醇包括双羟乙基-或双羟丙基-双酚A、环己烷二甲醇和双羟乙基氢醌。
也有利地用于异氰酸酯组分的是所谓的改性多官能异氰酸酯，即通过上述异氰酸酯化合物的化学反应获得的产物。示例性的是含有酯、脲、缩二脲、脲基甲酸酯并且优选地碳化二亚胺和/或脲酮亚胺的聚异氰酸酯。也可以使用含有碳化二亚胺基、脲酮亚胺基和/或异氰脲酸酯环的液体聚异氰酸酯，其异氰酸酯基(NCO)含量为12至40重量百分比，更优选地20至35重量百分比。这些包括例如基于以下的聚异氰酸酯：4,4'-2,4'-和/或2,2'-二苯基甲烷二异氰酸酯和对应的异构体混合物、2,4-和/或2,6-甲苯二异氰酸酯和对应的异构体混合物；二苯基甲烷二异氰酸酯和PMDI的混合物；以及甲苯二异氰酸酯和PMDI和/或二苯基甲烷二异氰酸酯的混合物。
通常，异氰酸酯组分的量可以根据合成皮革制品的实际需要而变化。例如，作为一个例示性实施方案，按用于制备预聚物的所有组分的总重量计，即按异氰酸酯组分(A)、异氰酸酯反应性组分(B)和催化剂(D)的总重量计，异氰酸酯组分的含量可以为约5wt％至约50wt％、优选地约10wt％至约40wt％、优选地约15wt％至约30wt％。
异氰酸酯反应性组分
在本申请中，术语“三羟基聚醚多元醇”、“三官能聚醚多元醇”和“羟基官能度为3.0的聚醚多元醇”可互换使用并且表示每个分子中包含大约三个羟基的聚醚多元醇。类似地，“二羟基聚醚多元醇”和“双官能聚醚多元醇”可以互换使用并以相同方式解释。
在本公开的各种实施方案中，异氰酸酯反应性组分(B)包含三羟基聚醚多元醇和可选地选自由以下项组成的组的一种或多种多元醇：包含至少两个羟基的脂肪族多元醇、包含至少两个羟基的脂环族或芳香族多元醇、包含至少两个羟基的芳脂族多元醇、除三羟基聚醚多元醇之外的聚醚多元醇(例如羟基官能度不等于3.0，诸如大于1.0至小于3.0、大于3.0至4.0、至多5.0、至多6.0、至多7.0或至多8.0的聚醚多元醇)、聚酯多元醇、具有至少两个羟基的植物油和它们的混合物。在本公开的各种实施方案中，三羟基聚醚多元醇具有3.0的官能度和1,500至12,000g/mol，优选地2,000至8,000g/mol，更优选地2,000至6,000g/mol的重均分子量(Mw)。优选地，除上述三羟基聚醚多元醇之外的多元醇选自由以下项组成的组：包含至少两个羟基的C2-C16脂肪族多元醇、包含至少两个羟基的C6-C15脂环族或芳香族多元醇、包含至少两个羟基的C7-C15芳脂族多元醇、分子量为100至5,000的聚酯多元醇、羟基官能度不等于3.0以及分子量为1,500至12,000的聚醚多元醇，以及它们的组合。根据优选的实施方案，除上述三羟基聚醚多元醇之外的多元醇为二羟基聚醚多元醇，即异氰酸酯反应性组分(B)可以是三羟基聚醚多元醇和二羟基聚醚的组合；更优选地，二羟基聚醚多元醇可以具有1,500至12,000g/mol，优选地2,000至8,000g/mol，更优选地2,000至6,000g/mol的分子量(Mw)。
在替代地实施方案中，异氰酸酯反应性组分还可以包含一种或多种不是聚醚多元醇的其他多元醇(诸如聚酯多元醇)或具有至少两个羟基的植物油。
在替代性实施方案中，异氰酸酯反应性组分是聚醚多元醇，其官能度(多元醇分子中异氰酸酯反应性基团特别是羟基的平均数)为1.0至3.0，并且重均分子量(Mw)为1,500至12,000g/mol、优选地2,000至8,000g/mol、更优选地2,000至6,000g/mol。
通常通过在存在催化剂的情况下选自环氧丙烷(PO)、环氧乙烷(EO)、环氧丁烷、四氢呋喃和它们的混合物的一种或多种环氧烷与适当的起始剂分子的聚合来制备聚醚多元醇。双官能聚醚多元醇通常由诸如环氧丙烷、环氧乙烷、环氧丁烷、四氢呋喃和它们的混合物的双官能原材料制备，而三官能聚醚多元醇的制备通常包括至少一种三羟基原材料，诸如1,2,3-丙三醇。典型的起始剂分子包括在分子中具有至少2个、优选地4至8个羟基或者具有两个或更多个伯胺基的化合物。合适的起始剂分子例如选自包含以下的组：苯胺、EDA、TDA、MDA和PMDA，更优选地选自包含以下的组：TDA和PMDA，最优选地TDA。当使用TDA时，所有异构体可以单独使用或以任何期望的混合物使用。例如，可以使用2,4-TDA、2,6-TDA、2,4-TDA和2,6-TDA的混合物、2,3-TDA、3,4-TDA、3,4-TDA和2,3-TDA的混合物以及所有上述异构体的混合物。借助于在分子中具有至少2个并且优选地2至8个羟基的起始剂分子，优选的是使用三羟甲基丙烷、甘油、季戊四醇、蓖麻油、糖化合物例如葡萄糖、山梨糖醇、甘露醇和蔗糖、多元酚、甲阶酚醛树脂诸如酚和甲醛的低聚缩合产物以及苯酚、甲醛和二烷醇胺的曼尼希缩合物，以及三聚氰胺。用于制备聚醚多元醇的催化剂可以包括用于阴离子聚合的碱性催化剂，诸如氢氧化钾，或用于阳离子聚合的路易斯酸催化剂，诸如三氟化硼。合适的聚合催化剂可以包括氢氧化钾、氢氧化铯、三氟化硼或双氰化物络合物(DMC)催化剂，诸如六氰基钴酸锌或季磷腈鎓化合物。在本公开的优选实施方案中，除三羟基聚醚多元醇之外的聚醚多元醇包括(甲氧基)聚乙二醇(MPEG)、聚乙二醇(PEG)、聚(丙二醇)以及具有伯羟基封端基团和仲羟基封端基团的环氧乙烷和环氧丙烷的共聚物。根据本公开的优选实施方案，三羟基聚醚多元醇包括1,2,3-丙三醇和环氧乙烷的共聚物；1,2,3-丙三醇与环氧丙烷的共聚物；1,2,3-丙三醇、具有伯羟基封端基团或仲羟基封端基团的环氧乙烷和环氧丙烷的共聚物。
通常，按用于在第一阶段制备预聚物的所有组分的总重量计，即按异氰酸酯组分(A)、异氰酸酯反应性组分(B)和催化剂(D)的总重量计，本文使用的异氰酸酯反应性组分的含量的范围可以为约35wt％至约95wt％、优选地约60wt％至约85wt％。
根据本申请的不同实施方案，按用于制备预聚物的所有组分的总重量计，即按异氰酸酯组分(A)，异氰酸酯反应性组分(B)和催化剂(D)的总重量计，异氰酸酯反应性组分(B)中所含的三羟基聚醚多元醇的含量的范围可以为约10wt％至约30wt％、优选地约10wt％至约25wt％、更优选地约10wt％至约20wt％。
根据本申请的优选实施方案，异氰酸酯反应性组分(B)是三羟基聚醚多元醇和除三羟基聚醚多元醇之外的附加的聚醚多元醇(诸如具有大于1.0至小于3.0，例如大于1.0至2.0的羟基官能度的聚醚多元醇)的组合，其中按用于制备预聚物的所有组分的总重量计，即按异氰酸酯组分(A)、异氰酸酯反应性组分(B)和催化剂(D)的总重量计，异氰酸酯反应性组分(B)中所含的上述“附加的”聚醚多元醇的含量的范围可以为约25wt％至约85wt％、优选地约45wt％至约85wt％、更优选地约55wt％至约75wt％。
催化剂
催化剂可以包括能够促进异氰酸酯基团和异氰酸酯反应性基团之间的反应的任何物质。不受理论的限制，催化剂可以包括例如：甘氨酸盐；叔胺；叔膦，诸如，三烷基膦和二烷基苄基膦；吗啉衍生物；哌嗪衍生物；各种金属的螯合物，诸如可以从乙酰丙酮、苯甲酰丙酮、三氟乙酰丙酮、乙酰乙酸乙酯等与金属(诸如Be、Mg、Zn、Cd、Pd、Ti、Zr、Sn、As、Bi、Cr、Mo、Mn、Fe、Co和Ni)获得的那些；强酸的酸性金属盐，诸如氯化铁、氯化锡；有机酸与各种金属(诸如，碱金属、碱土金属、Al、Sn、Pb、Mn、Co、Ni和Cu)的盐；有机锡化合物，诸如有机羧酸的锡(II)盐，例如，二乙酸锡(II)、二辛酸锡(II)、二乙基己酸锡(II)和二月桂酸锡(II)，以及有机羧酸的二烷基锡(IV)盐，例如，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；有机羧酸的铋盐，例如，辛酸铋；三价和五价As、Sb和Bi的有机金属衍生物以及铁和钴的羰基金属；或它们的混合物。
叔胺催化剂包括含有至少一个叔氮原子并且能够催化羟基/异氰酸酯反应的有机化合物。叔胺、吗啉衍生物和哌嗪衍生物催化剂可以包括，例如但不限于，三亚乙基二胺、四甲基亚乙基二胺、五甲基二亚乙基三胺、双(2-二甲基氨基乙基)醚、三乙胺、三丙胺、三丁胺、三戊胺、吡啶、喹啉、二甲基哌嗪、哌嗪、N-乙基吗啉、2-甲基丙二胺、甲基三亚乙基二胺、2,4,6-三二甲基氨基-甲基)苯酚、N,N’,N”-三(二甲基氨基-丙基)sym-六氢三嗪或它们的混合物。
通常，按用于制备预聚物的所有组分的总重量计，即按异氰酸酯组分(A)、异氰酸酯反应性组分(B)和催化剂(D)的总重量计，本文使用的催化剂的含量大于零且为至多1.0wt％、优选地至多0.5wt％、更优选地至多0.1wt％，诸如至多0.05wt％。
亲水性氨基硅氧烷化合物
亲水性氨基硅氧烷化合物是包含附接有含氮侧链和亲水性侧链的硅-氧主链的化合物。亲水氨基硅氧烷化合物的分子结构可以由式I表示：
Figure BDA0003275528990000101
其中每个R独立地表示甲基、乙基、正丙基、异丙基、正丁基、异丁基、仲丁基、叔丁基、正戊基、异戊基、叔戊基、新戊基、环己基、苯基、乙烯基、烯丙基或-(OCH2CH2)a-O-CH2-CH＝CH2；
R1是-(CH2)mNH2或-(CH2)s-NH-(CH2)tNH2；
R2是-CH2CH2CH2O(CH2CH2O)nH；并且
R3、R4、R5、R6和R7中的每一个独立地选自由甲基、乙基、正丙基、异丙基、正丁基、异丁基、仲丁基、叔丁基、正戊基、异戊基、叔戊基、新戊基、环己基和苯基组成的组；
其中a是1至10的整数，诸如1、2、3、4、5、6、7、8、9或10；x是20至200的整数，诸如20、30、40、50、60、70、80、90、100、110、120、130、140、150、160、170、180、190和200；y是1至10的整数，诸如1、2、3、4、5、6、7、8、9或10；z是1至10的整数，诸如1、2、3、4、5、6、7、8、9或10；m是1至5的整数，诸如1、2、3、4或5；s是1、2、3、4或5的整数；t是1、2、3、4或5的整数；并且n是5至20的整数，诸如5、6、7、8、9、10、11、12、13、14、15、16、17、18、19或20。
不受理论的限制，R1中的胺基和R2中的羟基可以与预聚物中剩余的异氰酸酯基团反应产生在聚氨酯主链中包含上述硅氧烷结构的聚氨酯，从而显著提高所得PU皮膜的性能特性(诸如抗粘性)。
根据本公开的一个优选实施方案，亲水性氨基硅氧烷化合物具有式II所示的结构：
Figure BDA0003275528990000111
其中R、R1、R2、x、y和z如上所述。
通常，按用于制备预聚物的所有组分的总重量计，即按异氰酸酯组分(A)、异氰酸酯反应性组分(B)和催化剂(D)的总重量计，本文所用的亲水性氨基硅氧烷化合物的含量为2wt％至10wt％、优选地2wt％至8wt％、更优选地2wt％至5wt％。可以看出，亲水性氨基硅氧烷化合物的含量是以预聚物的总量为100wt％计算的附加量。
需要注意的是，亲水性氨基硅氧烷化合物应首先经由混合而溶解/分散在水中得到水溶液，然后再脱气。在本发明中，氨基硅油在分散阶段加入，并且在预聚物合成阶段期间不加入聚合物主链中。原因是如果在预聚物合成阶段加入硅氧烷，则会形成一定程度的聚合物凝胶。
表面活性剂/乳化剂
根据优选的实施方案，水性聚氨酯分散体是外部乳化的分散体，即水性聚氨酯分散体优选地仅通过使用“外部表面活性剂/乳化剂”来制备且基本上不包含“内部表面活性剂/乳化剂”。
如本文所述的表述“外部乳化的聚氨酯分散体”是指包含有限量的内部乳化离子组分并且因此主要依赖于“外部表面活性剂/乳化剂”(即，在分散在液体介质中的聚氨酯颗粒内未与主链共价键合的离子或非离子乳化剂，尤其是通过由衍生自异氰酸酯基团与异氰酸酯反应性基团(诸如羟基)之间的反应的氨基甲酸酯键)的乳化功能以便稳定聚氨酯分散体的聚氨酯分散体。
根据本公开的一个实施方案，外部乳化的聚氨酯分散体通过以下步骤来制备：(i)使一种或多种单体的或预聚合的聚异氰酸酯与如上所述的异氰酸酯反应性组分(B)反应以形成包含氨基甲酸酯预聚物链和每个分子至少一个、优选地至少两个游离异氰酸酯基团的预聚物；(ii)在存在外部乳化剂的情况下将在步骤(i)中获得的预聚物分散在水性溶剂(例如水)中以形成乳液；以及可选地进一步将扩链剂和亲水性氨基硅氧烷化合物加入乳液中以与在步骤(i)中获得的预聚物反应并且形成外部乳化的聚氨酯分散体。根据本公开的一个实施方案，在步骤(i)中制备的预聚物不包含任何离子内部乳化剂或与氨基甲酸酯预聚物链共价键合的离子内部乳化剂的残留部分。根据本公开的另一个实施方案，在步骤(i)中制备的预聚物中的聚氨酯链不包含任何阳离子或阴离子侧基。
通过使用内部表面活性剂/乳化剂制备的PUD被称为“内部乳化的PUD”。根据现有技术的知识，用于制备内部乳化的PUD的典型工艺包括以下步骤：(i)使单体异氰酸酯或单体异氰酸酯的预聚物与多元醇和具有至少一个异氰酸酯反应性基团的阳离子或阴离子前体(即离子内部乳化剂)反应以形成包含与PU链附接的阳离子或阴离子亲水性侧基的PUD预聚物；(ii)可选地在这个步骤中在附加的外部乳化剂的辅助下，将PUD预聚物分散到水性溶剂(例如水)中，其中与PU链附接的阳离子或阴离子亲水性基团作为主乳化剂；以及可选地(iii)使乳液与附加的扩链剂反应以形成离子内部乳化的聚氨酯分散体。可以清楚地看到，本公开中使用的外部乳化的PUD与现有技术中的离子内部乳化的PUD在制备工艺和所得到的聚氨酯颗粒的组成方面完全不同。需要说明的是，本申请制备的聚氨酯颗粒包含扩链剂的残基和与聚氨酯主链附接的亲水性氨基硅氧烷化合物，但这些残基至少在电荷中性方面与上述离子内部乳化官能团不同，并且因此应排除在离子内部乳化官能团的定义之外。此外，在优选的实施方案中，聚氨酯的乳化主要通过或仅通过使用外部乳化剂来进行，并且在形成PU乳液之前不加入扩链剂和亲水性氨基硅氧烷化合物。这就是本公开的PU分散体被确定为外部乳化体系的原因。
在本公开的一个实施方案中，在制备外部乳化的PUD期间不加入上述离子内部乳化组分(乳化剂)。在本公开的优选实施方案中，外部乳化的聚氨酯分散体在分散在外部乳化的PUD中的聚氨酯预聚物颗粒的主链中不含阴离子或阳离子盐基团。
本公开的水性聚氨酯分散体可以使用任何阴离子表面活性剂、阳离子表面活性剂、两性表面活性剂或非离子表面活性剂来制备。合适的表面活性剂类别包括但不限于：乙氧基化酚的硫酸盐，诸如聚(氧基-1,2-乙烷二基)α-磺基-ω(壬基苯氧基)盐；碱金属脂肪酸盐，诸如碱金属油酸盐和硬脂酸盐；碱金属C12-C16烷基硫酸盐，诸如碱金属月桂基硫酸盐；胺C12-C16烷基硫酸盐，诸如胺月桂基硫酸盐，更优选地三乙醇胺月桂基硫酸盐；碱金属C12-C16烷基苯磺酸盐，诸如支链的和直链的十二烷基苯磺酸钠；胺C12-C16烷基苯磺酸盐，诸如三乙醇胺十二烷基苯磺酸盐；阴离子和非离子氟碳乳化剂，诸如氟化C4-C16烷基酯和碱金属C4-C16全氟烷基磺酸盐；有机硅乳化剂，诸如改性聚二甲基硅氧烷。优选地，表面活性剂是可以与存在于中性盐中的多价阳离子反应以形成有机酸的不溶性多价阳离子水不溶性盐的表面活性剂。示例性优选的表面活性剂包括十八烷基磺基琥珀酸二钠、十二烷基苯磺酸钠、硬脂酸钠和硬脂酸铵。
根据本公开的实施方案，按用于制备预聚物的所有组分的总重量计，即按异氰酸酯组分(A)、异氰酸酯反应性组分(B)和催化剂(D)的总重量计，表面活性剂的含量大于零且不超过10wt％、优选地不超过5wt％、更优选地不超过3.5wt％。可以看出，表面活性剂的含量是以预聚物的总量为100wt％计算的附加量。
扩链剂
根据本公开的一个实施方案，扩链剂可以是二胺或具有另一异氰酸酯反应性基团的胺化合物，但优选地选自由以下项组成的组：胺化聚醚二醇；哌嗪；氨基乙基乙醇胺；包含至少两个胺基团的C2-C16脂肪族多胺，例如乙二胺；包含至少两个胺基团的C4-C15脂环族或芳族多胺，诸如环己二胺和对二甲苯二胺；包含至少两个胺基团的C7-C15芳脂族多胺；胺化的C2-C8醇，例如乙醇胺；以及它们的混合物。根据优选的实施方案，扩链剂是具有官能度2并包含伯胺基团或仲胺基团的多胺。根据本公开的一个实施方案，扩链剂包括具有刚性主链的脂肪胺，并且扩链剂的优选实例包括哌嗪、环己二胺和对二甲苯二胺。优选地，将胺扩链剂溶解在用于制备PU分散体的水中。
根据本公开的实施方案，按用于在第一阶段制备预聚物的所有组分的总重量计，即按异氰酸酯组分(A)、异氰酸酯反应性组分(B)和催化剂(D)的总重量计，扩链剂的含量为1.0wt％至15wt％、优选地2wt％至10wt％、更优选地3wt％至9wt％。可以看出，扩链剂的含量是以预聚物的总量为100wt％计算的附加量。
水性聚氨酯分散体
根据本申请的实施方案，水性聚氨酯分散体通过两步反应制备。在第一阶段，通过在存在催化剂(D)的情况下使异氰酸酯组分(A)中的异氰酸酯基团与异氰酸酯反应性组分(B)中的异氰酸酯反应性基团反应来制备预聚物。通过上述反应可以在预聚物中形成聚氨酯主链。在第二阶段，将预聚物与表面活性剂(E)混合并与扩链剂(F)和亲水性氨基硅氧烷化合物(C)反应。扩链剂(F)和亲水性氨基硅氧烷化合物(C)包含异氰酸酯反应性基团，例如胺基团，它们与预聚物中残留的游离异氰酸酯基团反应，因此它们的结构部分也被引入到所得聚氨酯主链中。在第二阶段期间，预聚物的链被扩链剂(F)和亲水性氨基硅氧烷化合物(C)进一步扩链以形成包含分散在水中的聚氨酯颗粒的水性聚氨酯分散体。水性聚氨酯分散体可以加热并干燥以形成表现出优异的改进的性能特性的皮膜，所述优异的改进的性能特性诸如增强的色牢度、改善的低温稳定性、良好的抗粘性、巴利耐弯曲性、耐磨性和机械性质。
水性聚氨酯分散体可以具有聚氨酯颗粒的任何合适的固体负载，但是通常固体负载为总分散体重量的约1重量％到约70重量％固体、优选地至少约2重量％、更优选地至少约4重量％、更优选地至少约6重量％、更优选地至少约15重量％、更优选地至少约25重量％、更优选地至少约35重量％、最优选地至少约40重量％到至多约70重量％、优选地至多68重量％、更优选地至多约65重量％、更优选地至多约60重量％并且最优选地至多约50重量％。
水性聚氨酯分散体还可以含有流变改性剂，诸如增强分散体的分散性和稳定性的增稠剂。可以使用任何合适的流变改性剂，如本领域已知的流变改性剂。优选地，流变改性剂是不会引起分散体变得不稳定的流变改性剂。更优选地，流变改性剂是未被离子化的水溶性增稠剂。有用的流变改性剂的实例包括甲基纤维素醚、碱溶胀性增稠剂(例如，钠或铵中和的丙烯酸聚合物)、疏水改性的碱溶胀性增稠剂(例如，疏水改性的丙烯酸共聚物)和缔合性增稠剂(例如，疏水改性的基于环氧乙烷的氨基甲酸酯嵌段共聚物)。优选地，流变改性剂是甲基纤维素醚。增稠剂的量为水性聚氨酯分散体的总重量的至少约0.2重量％到约5重量％、优选地约0.5重量％到约2重量％。
通常，水性聚氨酯分散体所具有的粘度为至少约10cp到至多约10,000cp、优选地至少约20cp到至多约5000cp、更优选地至少约30cp到至多约3000cp。
在本公开的实施方案中，可以通过表面活性剂和高剪切搅拌作用促进PU颗粒在水性聚氨酯分散体中的分散，其中剪切力和搅拌速度可以根据具体需要适当调整。
根据本公开的一个实施方案，水性聚氨酯分散体还可以包含一种或多种颜料、染料和/或着色剂，所有颜料、染料和/或着色剂在本公开中通常被称为“色母料”。例如，可以加入色母料，以便对透明或半透明膜赋予期望的颜色。颜料、染料和/或着色剂的实例可以包括氧化铁、氧化钛、碳黑以及它们的混合物。按水性聚氨酯分散体的总重量计，颜料、染料和/或着色剂的量可以为0.1重量％到15重量％、优选地0.5-10重量％、更优选地1重量％到5重量％。可用于本发明的合适的可商购获得的黑色颜料可以包括例如可从朗盛德国有限责任公司(Lanxess Deutschland GmbH)获得的EUDERMTM黑色B-N碳黑分散体。
根据本公开的一个实施方案，水性聚氨酯分散体还可以包含选自由以下项组成的组的其他添加剂：增稠剂(诸如丙烯酸)、快干剂(诸如丙二醇)、消泡剂(诸如有机硅)，以及它们的任何组合。
不受任何理论的限制，认为在预聚物的合成期间引入了与三官能聚醚多元醇的一定交联度，以及在PUD的制备期间引入了刚性脂肪族扩链剂和由式I助扩链剂表示的亲水性氨基硅油可以显著改善所得聚氨酯皮层的性能特性(诸如增强的色牢度、改善的低温稳定性、良好的抗粘性、巴利耐弯曲性、耐磨性和机械性质)。
层压合成革制品
图1是本文所述的合成皮革制品的一个实施方案的横截面的示意图。在本发明的一个实施方案中，合成皮革制品从上到下包含由水性聚氨酯分散体形成的顶部皮膜、2K PU泡沫基层和背衬基材(例如纺织布)。请注意，皮革制品不一定以实际比例示出，并且一层或多层的尺寸可能被夸大以使得清楚地示出所述皮革制品的配置。
本公开所使用的2K PU泡沫优选为非溶剂PU泡沫，并且包含在其中限定多个孔和/或泡孔的连续PU基质。如本文所公开的，术语“无溶剂(solvent free)”、“无溶剂(solventless)”或“非溶剂”可以互换地用于描述PU泡沫或任何其他分散体、混合物等，并且应当解释为按原材料的混合物的总重量计，用于制备PU泡沫或PU分散体的所有原材料的混合物包含小于3重量％、优选地小于2重量％、优选地小于1重量％、更优选地小于0.5重量％、更优选地小于0.2重量％、更优选地小于0.1重量％、更优选地小于100ppm重量份、更优选地小于50ppm重量份、更优选地小于10ppm重量份、更优选地小于1ppm重量份的任何有机溶剂或无机溶剂。如本文所公开的，术语“溶剂”是指其功能是仅溶解一种或多种固体、液体或气体材料而不会引发任何化学反应的有机液体和无机液体。换句话说，尽管在聚合技术中通常被认为是“溶剂”的一些有机化合物，例如乙二醇和丙二醇以及水用于制备2K PU泡沫，但是它们都不属于“溶剂”，因为它们通过引发化学反应主要充当异氰酸酯反应性功能性物质、扩链剂或发泡剂等。
根据本公开的一个实施方案，2K PU泡沫层所具有的厚度在0.01μm到2,000μm的范围内，优选地在0.05μm到1,000μm的范围内，更优选地在0.1μm到750μm的范围内并且更优选地在0.2μm到600μm的范围内。
根据本公开的一个实施方案，用无溶剂聚氨酯体系制备2K聚氨酯泡沫层中的发泡聚氨酯，所述无溶剂聚氨酯体系包含：(i)一种或多种第二异氰酸酯组分，(ii)一种或多种第二异氰酸酯反应性组分，(iii)一种或多种发泡剂、第二催化剂和任何其他添加剂。第二异氰酸酯组分(i)包括一种或多种用于异氰酸酯组分(A)的聚异氰酸酯和/或异氰酸酯预聚物。第二异氰酸酯反应性组分(ii)包含具有选自以下的两个或更多个异氰酸酯反应性基团的化合物：OH基团、SH基团、NH基团、NH2基团和碳酸基团，例如β-二酮基团。根据本申请的一个实施方案，异氰酸酯反应性组分(ii)包含用于(B)的那些。在本公开的一个优选实施方案中，第二异氰酸酯组分(i)和第二异氰酸酯反应性组分(ii)在存在发泡剂/起泡剂的情况下彼此反应，并且发泡剂与异氰酸酯反应性组分组合使用。有用的发泡剂包括通常已知的化学或物理反应性化合物。物理起泡剂可以选自由以下组成的组中的一种或多种：二氧化碳、氮气、稀有气体、具有4到8个碳原子的(环)脂肪族烃、二烷基醚、酯、酮、缩醛和具有1到8个碳原子的氟代烷烃。化学反应性起泡剂优选地包含水，其优选地作为与异氰酸酯反应性组分(ii)的共混物的成分而被包含在内。按用于制备2K PU泡沫层的所有原材料的总重量计，发泡剂的量在0.05到10重量％的范围内，优选地在0.1到5重量％的范围内，更优选地为0.1到2重量％并且最优选地为0.1到0.5重量％。2K PU层的密度通常为0.3到1.1千克/升，并且密度优选地为0.4到0.9千克/升。
在本公开的实施方案中，按用于制备2K PU泡沫层的所有原材料的总重量计，第二异氰酸酯组分(i)与第二异氰酸酯反应性组分(ii)在存在选自有机锡化合物(诸如二乙酸锡、二辛酸锡、二月桂酸二丁基锡和/或强碱性胺，诸如二氮杂双环辛烷、三乙胺、三亚乙基二胺或双(N,N-二甲基氨基乙基)醚)的催化剂的情况下反应，所述催化剂的量为0.01重量％到5重量％、优选地0.05重量％到4重量％、更优选地0.05重量％到3重量％。
在本公开的实施方案中，特别选择第二异氰酸酯组分(i)和第二异氰酸酯反应性组分(Bii)的类别和摩尔含量，使得NCO基团与NCO反应性氢原子(例如，羟基中的氢原子)的总当量比在0.9:1到1.8:1的范围内，优选地在0.92:1到1.6:1的范围内，优选地在0.95:1到1.5:1的范围内并且更优选地在1:1到1.45:1的范围内，更优选地在1.05:1到1.4:1的范围内并且更优选地在1.10:1到1.35:1的范围内。
释放层
合适的释放层在现有技术中通常被称为“离型纸”。合适的释放层的实例包括金属箔、塑料箔或纸箔。在本公开的一个优选实施方案中，释放层是可选地用塑料膜涂覆的纸层。优选地，用聚烯烃、更优选地用聚丙烯涂覆本文公开的纸层。可替代地，优选地用硅酮涂覆纸层。在替代性实施方案中，本文所使用的释放层是可选地用塑料膜涂覆的PET层。优选地，可以用聚烯烃、更优选地用聚丙烯涂覆PET层。可替代地，优选地用硅酮涂覆PET层。合适的释放层的实例是可商购获得的。本公开中使用的释放层可以具有平坦的、压花的或图案化的表面，使得可以在合成皮革制品的最外表面上形成对应的或互补的表面轮廓。优选地，释放层以皮革纹理的模式纹理化，从而对合成皮革制品赋予与高级天然皮革相当的良好触觉性质。释放层的厚度通常为0.001mm到10mm、优选地0.01mm到5mm并且更优选地0.1mm到2mm。
只要释放层能够耐受在制造过程期间经历的化学反应、机械加工和热处理，并且可以容易地从所得到的合成皮革上剥离而不引起皮膜与2K PU泡沫基层之间的分层，就可以适当地调整释放层的材料和厚度。
助剂和添加剂
PU皮膜和2K PU泡沫基层可以独立地且可选地包含用于特定目的的任何附加的助剂和/或添加剂。
在本公开的一个实施方案中，一种或多种助剂和/或添加剂可以选自由以下项组成的组：填充剂、泡孔调节剂、释放剂、着色剂/颜料、表面活性化合物、手感剂、消光剂、增稠剂、交联剂和稳定剂。
合适的填充剂的实例包括玻璃纤维、矿物纤维、天然纤维(诸如亚麻、黄麻或剑麻)，例如玻璃鳞片、硅酸盐(诸如云母(mica)或云母(glimmer))、盐(诸如碳酸钙、白垩或石膏)。按皮膜或2K PU泡沫层的总干重计，填充剂通常以0.5重量％到60重量％、优选地3重量％到30重量％并且更优选地3重量％到10重量％的量使用。
背衬基材
在本公开的实施方案中，背衬基材的厚度在0.01mm到50mm的范围内，优选地在0.05mm到10mm的范围内并且更具体地在0.1mm到5mm的范围内。背衬基材可以包括选自由以下组成的组中的一种或多种：织物，优选地织造或非织造织物、浸渍织物、针织织物、编织织物或微纤维；金属箔或塑料箔，例如橡胶、PVC或聚酰胺；以及皮革，优选地剖层皮革。
背衬基材可以由织造或非织造纺织品制成。优选地，纺织品是非织造纺织品。纺织品可以通过任何合适的方法制造，如本领域中已知的方法。纺织品可以由任何合适的纤维材料制备。合适的纤维材料包括但不限于合成纤维材料和天然纤维材料或半合成纤维材料及其混合物或共混物。合成纤维材料的实例包括聚酯、聚酰胺、丙烯酸树脂、聚烯烃、聚氯乙烯、聚偏二氯乙烯、聚乙烯醇及其共混物或混合物。天然的半合成纤维材料的实例包括棉、羊毛和大麻。
制造技术
水性聚氨酯分散体可以通过常规的涂覆技术，诸如喷涂、刮涂、模涂、铸涂等进行施涂。
在施涂下一层之前，可以将皮膜部分地或完全地干燥。优选地，将皮膜完全地干燥，以便使其中截留的水分最小化，并且然后在其上施涂下一层。在本申请的替代性实施方案中，仅从释放层上的皮膜去除一部分水分，然后将皮膜与在其上施涂的2K PU泡沫层一起完全地干燥。
根据一个实施方案，将用于2K非溶剂PU泡沫的第二异氰酸酯组分(i)和第二异氰酸酯反应性组分(ii)混合在一起，施涂到皮膜，并且通过在例如70℃到120℃、优选地75℃到110℃的温度下在烘箱中加热持续10秒到5分钟、更优选地30秒到2分钟、更优选地45到90秒的短持续时间来预固化。然后在加压辊的辅助下，将背衬基材(例如纺织品织物)施涂到预固化的2K PU泡沫层，然后在例如100℃至160℃、优选地110℃至150℃的较高温度下后固化持续3至20分钟、优选地3至15分钟，更优选地4至10分钟的较长持续时间。上述两步固化工艺旨在确保预固化的2K PU泡沫与背衬基材之间的高粘附强度。
根据本公开的优选实施方案，在2K PU泡沫已经完全固化之后去除释放层。释放层可以经由任何普通技术剥离。
根据本公开的优选实施方案，在去除释放层之后，可以将顶部终饰层施涂到合成皮革的表面上(即，皮膜的最外表面上)并且干燥以形成保护膜层。终饰层的存在可以进一步提高多层合成皮革的耐磨性。可以通过使用任何合适的原材料和技术来形成保护膜层。终饰层可以可选地包含添加剂，诸如润湿剂、交联剂、粘合剂、消光剂、手感改性剂、颜料和/或着色剂、增稠剂或用于皮膜的其他添加剂。本文公开的合成皮革还可以包含一个或多于一个的可选的附加层，诸如皮膜与终饰层之间的颜色层。其他合适的可选的附加层可以选自防水层、UV保护层和触觉(触摸/感觉)改性层。本发明的工艺可以连续地或分批地进行。
本文公开的多层结构合成皮革可以被切割或以其他方式成形，从而具有适用于任何期望目的(诸如鞋子制造)的形状。根据预期应用，可以与天然皮革类似地对合成皮革进行进一步处理或后处理，例如通过刷涂、填充、碾磨或熨烫。如果需要，合成皮革(如天然皮革)可以用常规终饰组合物进行终饰。这提供了控制其特性的进一步可能性。本文公开的多层结构可以用于特别适合用作合成皮革的各种应用中，例如鞋类、手提包、皮带、钱包、服装、家具装饰品、汽车装饰品和手套。多层结构特别适用于汽车应用。
实施例
现在将在以下实施例中描述本发明的一些实施方案，除非另外说明，否则其中所有份数和百分比均以重量计算。
下表1中列出了实施例中使用的原材料的信息：
表1.实施例中使用的原材料
Figure BDA0003275528990000211
Figure BDA0003275528990000221
通过使用表2中列出的原材料来制备2K非溶剂PU泡沫。
表2. 2K PU复合材料中使用的原材料
材料 剂量(份)
SPECFLEX NR 1156配制多元醇 100
SPECFLEX NE 1156异氰酸酯 58
Polycat SA2LE 0.05
Polycat SA-8 0.2
Formrez UL-29 0.03
在以下本发明实施例和比较实施例中，通过以下步骤1)至4)制备包含衍生自水性聚氨酯分散体的皮膜和2K PU泡沫基层的合成皮革制品。
1)水性聚氨酯分散体的预聚物的制备
将Voranol 222-056、Voranol 4000LM多元醇、Voranol 3010多元醇和MPEG1000装入1000ml三颈烧瓶中，并在115℃、76mmHg压力下脱水一小时，然后自然冷却至约72℃。在氮气(N2)流的保护和机械搅拌下，在约72℃下将IPDI倒入脱水的多元醇混合物中，然后将催化剂DABCO MB20加入烧瓶中。反应在约72℃下持续一小时，然后加热至约82℃的温度并继续另外的2.5小时。将产物封装在塑料瓶中并在氮气保护下密封储存。每个比较实施例和本发明实施例中使用的所有组分的含量汇总于表4中。可以看出多元醇组分的总量保持在恒定水平，因此可以计算出所得预聚物的理论NCO％为7.5wt％。
2)水性聚氨酯分散体的制备
将上述步骤1)中制备的100克预聚物倒入500ml塑料杯中，并用考尔斯混合器(cowles mixer)搅拌。在约4000rpm的混合速度下，将13g的23wt％SDBS水溶液逐渐加入到预聚物中。再搅拌几分钟后，在约4000rpm的混合速度下将冰水逐滴加入预聚物中。加入冰水后发生相反转并形成水包油乳液。然后将混合速度降低到约1500rpm。将脱气过夜的氨基硅氧烷化合物(亲水性OFX-7700)和哌嗪的水溶液逐滴加入乳液中。将所有这些加入溶液后，再继续机械搅拌12分钟。最后，获得具有约50％固体含量的聚氨酯分散体，并将其储存在带盖的塑料容器中。
3)PUD皮膜的制备
称取2)中制备的聚氨酯分散体22.5克，并用等量的去离子水稀释。将稀释的PUD转移到真空烘箱中并脱气约10分钟。然后将脱气的PUD倒入塑料表面培养皿中。将填充有PUD的平皿转移到烘箱中，并在48℃下加热24小时，然后将膜从平皿上剥离、翻转并再继续干燥24小时。将膜冷却至室温以进行拉伸和撕裂测试。
4)合成皮革制品的制造
将2)中制备的水性聚氨酯分散体与表3中示出的色母料、增稠剂、增滑剂和快干剂在高速(1000至3000rpm)下混合几分钟。将配制的PUD涂覆在离型纸上至湿膜厚度为100μm。将涂覆的离型纸在烘箱中在95℃下干燥2min，再用配制的PUD重新涂覆至湿膜厚度为100μm，在烘箱中在95℃下干燥2min，并且然后在110℃下干燥2min。将具有干燥的PU表层的离型纸从烘箱中取出并冷却至环境温度。将配制的2K PU复合材料涂覆在离型纸上经干燥的PU皮膜上至湿膜厚度为300μm。将带有PU皮膜的离型纸和经涂覆的2K PU复合材料转移到100℃的烘箱中并预固化75秒。然后将背衬基材(纺织布)小心地施加到2K PU泡沫层上，并用3.5kg辊压制2次。将试样放入140℃烘箱中并后固化4分钟，然后取出冷却。
表3.步骤4)中使用的原材料
材料 剂量(份)
PUD 50.2
Black B-N 3
RM 998 0.2
S2229 2.5
DC-8590 0.05
Bi Cat 8840 0.10
表征产品的技术
(a)步骤3)中形成的PUD膜的机械性质
根据标准ASTM D412-15a表征在步骤3)中获得的PUD膜的拉伸强度、断裂伸长率、100％伸长率下的模量以及撕裂强度。一般来说，对于合成皮革应用(尤其是用于沙发和鞋的合成皮革)，或大于10Mpa的拉伸强度、大于500％的伸长率以及大于2.5MPa的100％伸长率下的模量是合乎需要的。
(b)步骤4)中制备的合成皮革制品的抗粘性能特性
根据GB/T 8948-2008标准表征在上述步骤4)中制备的合成皮革制品的抗粘性。特别地，将两个90mm×60mm的合成皮革制品样品在1kg的压力下面对面粘贴在一起，并在85℃的烘箱中加热3小时。根据在室温下分离过程中两个样品之间的粘性程度对抗粘性进行从1到5的分级：
等级1：完全不粘；
等级2：可以用少量力分离；
等级3：可以用一定的力分离并且不破坏表面；
等级4：可以用大的力分离并且表面出现不完全损坏；以及
等级5：无法分离。
(c)步骤4)中制备的合成皮革制品的湿色牢度
根据标准：ISO-11640测量步骤4)中制备的合成皮革制品的湿色牢度。特别地，在测量仪器的摩擦头末端装有浸湿的湿白色羊毛毡(15mm×15mm)。羊毛毡在皮革样品(120mm×40mm)上以1kg的负荷来回摩擦(摩擦距离为37mm)。湿色牢度是根据白色羊毛毡的颜色在50次摩擦循环后是否发生变化来评价的。
合格：50次摩擦循环后颜色没有变化。
不合格：50次摩擦循环后颜色发生变化。
(d)步骤2)中制备的PUD的低温稳定性
根据客户要求对步骤2)中制备的PUD的低温稳定性进行测试。特别地，PUD在4℃下的冰箱中储存2周，然后使PUD在室温(20℃)下解冻。根据PUD的最终状态评价低温稳定性。
合格：PUD恢复为最终粘度小于1000cp的液体。
不合格：PUD不能恢复为液体或恢复为最终粘度高于1000cp的液体。
(e)步骤4)中制备的合成皮革制品的巴利耐弯曲性
根据标准：QB-T 2714-2005对步骤4)中制备的合成皮革制品的巴利耐弯曲性进行表征。特别地，使用皮革挠曲测试仪来测量从步骤4)中制备的合成皮革切下的试样(70mm×45mm)的巴利耐弯曲性。将试样底端固定，并折叠上端，并且然后展开。在上述折叠/展开循环的某些时间之后，检查试样是否有任何损坏。
合格：在室温(20℃)下50000次折叠/展开循环和在-15℃下30000次折叠/展开循环后，试样均未损坏。
不合格：在室温(20℃)下50000次折叠/展开循环或在-15℃下30000次折叠/展开循环后，试样损坏。
比较实施例1-3和本发明实施例1-2的配制物和表征结果汇总在表4中。本发明实施例与比较实施例的区别在于，比较实施例要么不包含用于合成预聚物的三官能聚醚多元醇(Voranol 3010多元醇)，或者要么包含低于或高于优选的三官能聚醚多元醇含量的含量。具体来说，比较实施例1仅包含双官能聚醚多元醇(Voranol 222-056多元醇和Voranol4000LM多元醇)，而比较实施例2和3包含5wt％或30wt％的三官能聚醚多元醇(Voranol3010多元醇)，其超出了本申请中限定的10-20wt％的优选范围。另一方面，本发明实施例1和2分别包含10wt％和20wt％的三官能聚醚多元醇(Voranol 3010多元醇)。在这些比较实施例和本发明实施例中，双官能聚醚多元醇(Voranol 222-056和Voranol4000LM)的相对量略有调整，以便将目标预聚物中的EO％保持在大约恒定的水平(5-6％)。包括表面活性剂、水和扩链剂包的剂量的这些实施例的PUD分散体配制物都是相同的。刚性脂肪族二胺哌嗪用作主扩链剂以提高PUD膜的机械性质，包括拉伸强度和100％伸长率下的模量。亲水性氨基硅油OFX-7700用作助扩链剂，以改善最终合成皮革的抗粘性。
比较实施例1-3与本发明实施例1-2之间的比较说明了来源于三官能聚醚多元醇(Voranol 3010多元醇)的引入以及其特别设计的含量的技术效果。所有样品均表现出抗粘等级为1，这代表优异的抗粘性能并且能够满足合成皮革制造商和客户的要求。然而，没有一个比较实施例能够同时满足所有对机械性质(拉伸强度、伸长率、100％伸长率下的模量)、低温稳定性、抗粘性、巴利耐弯曲性和色牢度的要求。
表4.比较实施例1-3和本发明实施例1-2的配制物和表征结果
Figure BDA0003275528990000281
本发明实施例1和2与比较实施例1和2之间的比较表明，与不通过使用三官能聚醚多元醇或较低量的三官能聚醚多元醇制备的比较预聚物相比，通过使用10-20wt％的三官能聚醚多元醇制备的预聚物可以实现PUD的低温稳定性和合成皮革皮层的湿色牢度的显著改善。同时，本发明实施例1和2仍表现出良好的机械性质(拉伸强度和伸长率)和巴利耐弯曲性。
本发明实施例1和2与比较实施例3之间的比较表明，与通过使用较高量的三官能聚醚多元醇制备的比较预聚物相比，通过使用10-20wt％的三官能聚醚多元醇制备的预聚物可以实现合成皮革皮层的巴利耐弯曲性的显著改善。同时，与比较实施例3相比，本发明实施例1和2表现出好得多的机械性质(伸长率)。
比较实施例4-7
比较实施例4至7通过重复本发明实施例1的程序进行，不同之处在于采用下表5和表6中所示的配制物。
表5.比较实施例4-7的配制物和表征结果
Figure BDA0003275528990000291
Figure BDA0003275528990000301
表6.比较实施例4至7的合成皮革表皮层配制物
材料 剂量(份)
PUD 93
Black B-N 5
PG(1,2-丙二醇) 5
RM 825 2
A2添加剂 0.5
可以看出，所有这些不包含三官能聚醚多元醇的比较实施例均表现出较差的低温稳定性和湿色牢度。

Claims (13)

1.一种水性聚氨酯分散体，所述水性聚氨酯分散体包含分散在水中的聚氨酯颗粒，其中所述水性聚氨酯分散体衍生自以下物质的反应：
(A)包含一种或多种具有至少两个异氰酸酯基团的化合物的异氰酸酯组分；
(B)包含一种或多种具有至少两个异氰酸酯反应性基团的化合物的异氰酸酯反应性组分，其中所述异氰酸酯反应性组分包含羟基官能度为3.0以及重均分子量为1,500至12,000g/mol的聚醚多元醇；
(C)由式I表示的亲水性氨基硅氧烷化合物：
Figure FDA0003275528980000011
其中每个R独立地表示甲基、乙基、正丙基、异丙基、正丁基、异丁基、仲丁基、叔丁基、正戊基、异戊基、叔戊基、新戊基、环己基、苯基、乙烯基、烯丙基或-(OCH2CH2)a-O-CH2-CH＝CH2；
R1是-(CH2)mNH2或-(CH2)s-NH-(CH2)tNH2；
R2是-CH2CH2CH2O(CH2CH2O)nH；并且
R3、R4、R5、R6和R7中的每一个独立地选自由甲基、乙基、正丙基、异丙基、正丁基、异丁基、仲丁基、叔丁基、正戊基、异戊基、叔戊基、新戊基、环己基和苯基组成的组；
其中a是1至10的整数；x是20至500的整数；y是1至10的整数；z是1至10的整数；m是1至5的整数；s是整数1、2、3、4或5；t是整数1、2、3、4或5；并且n是5至20的整数；并且其中按所述异氰酸酯组分(A)、所述异氰酸酯反应性组分(B)和催化剂(D)的总重量计，所述亲水性氨基硅氧烷化合物(C)的含量为2.0wt％至10wt％；
(D)催化剂；
(E)表面活性剂；
(F)扩链剂；以及
(G)水。
2.根据权利要求1所述的水性聚氨酯分散体，其中不存在与所述聚氨酯颗粒中的聚氨酯的主链共价附接的阳离子或阴离子亲水侧基，或能够转化为与所述聚氨酯颗粒中的聚氨酯的主链共价附接的所述阳离子或阴离子亲水侧基的基团，并且所述聚氨酯被外部乳化。
3.根据权利要求1或权利要求2所述的水性聚氨酯分散体，其中所述一种或多种具有至少两个异氰酸酯基团的化合物选自由以下项组成的组：
a)包含至少两个异氰酸酯基团的C4-C12脂肪族聚异氰酸酯、包含至少两个异氰酸酯基团的C6-C15脂环族或芳香族聚异氰酸酯、包含至少两个异氰酸酯基团的C7-C15芳脂族聚异氰酸酯以及它们的组合；以及
b)通过使a)的一种或多种聚异氰酸酯与选自由以下项组成的组的一种或多种异氰酸酯反应性组分反应来制备的异氰酸酯预聚物：包含至少两个羟基的C2-C16脂肪族多元醇、包含至少两个羟基的C6-C15脂环族或芳香族多元醇、包含至少两个羟基的C7-C15芳脂族多元醇、分子量为500至5,000的聚酯多元醇、分子量为200至5,000的聚碳酸酯二醇、分子量为200至5,000的聚醚二醇、羟基官能度为3.0以及重均分子量为1,500至12,000g/mol的聚醚多元醇、包含至少两个氨基的C2至C10聚胺、包含至少两个硫醇基的C2至C10聚硫醇、包含至少一个羟基和至少一个氨基的C2-C10烷醇胺以及它们的组合，条件是所述异氰酸酯预聚物包含至少两个游离异氰酸酯端基。
4.根据权利要求1所述的水性聚氨酯分散体，其中按所述异氰酸酯组分(A)、所述异氰酸酯反应性组分(B)和所述催化剂(D)的总重量计，所述异氰酸酯组分(A)的含量为5wt％至50wt％。
5.根据权利要求1或2所述的水性聚氨酯分散体，其中所述一种或多种具有至少两个异氰酸酯反应性基团的化合物选自由以下项组成的组：包含至少两个羟基的C2-C16脂肪族多元醇、包含至少两个羟基的C6-C15脂环族或芳香族多元醇、包含至少两个羟基的C7-C15芳脂族多元醇、分子量为500至5,000的聚酯多元醇、分子量为200至5,000的聚碳酸酯二醇、分子量为200至5,000的聚醚二醇、羟基官能度为3.0以及重均分子量为1,500至12,000g/mol的聚醚多元醇、包含至少两个氨基的C2至C10聚胺、包含至少两个硫醇基的C2至C10聚硫醇、包含至少一个羟基和至少一个氨基的C2-C10烷醇胺、具有至少两个羟基的植物油以及它们的组合。
6.根据权利要求1或2所述的水性聚氨酯分散体，其中按所述异氰酸酯组分(A)、所述异氰酸酯反应性组分(B)和所述催化剂(D)的总重量计，所述异氰酸酯反应性组分(B)的含量为35wt％至95wt％。
7.根据权利要求1或2所述的水性聚氨酯分散体，其中按所述异氰酸酯组分(A)、所述异氰酸酯反应性组分(B)和所述催化剂(D)的总重量计，所述羟基官能度为3.0以及重均分子量为1,500至12,000g/mol的聚醚多元醇的含量为10wt％至20wt％。
8.根据权利要求1或2所述的水性聚氨酯分散体，其中所述催化剂(D)选自由以下项组成的组：有机锡化合物、有机铋化合物、叔胺、吗啉衍生物、哌嗪衍生物以及它们的组合；并且
其中按所述异氰酸酯组分(A)、所述异氰酸酯反应性组分(B)和所述催化剂(D)的总重量计，所述催化剂(D)的含量为1.0wt％或更少。
9.根据权利要求1或2所述的水性聚氨酯分散体，其中所述表面活性剂(E)选自由以下项组成的组：聚(氧-1,2-乙二基)α-磺基-ω(壬基苯氧基)盐、碱金属油酸盐和硬脂酸盐、碱金属C12-C16烷基硫酸盐、胺C12-C16烷基硫酸盐、碱金属C12-C16烷基苯磺酸盐、胺C12-C16烷基苯磺酸盐、氟化C4-C16烷基酯、碱金属C4-C16全氟烷基磺酸盐以及它们的组合；并且
其中按所述异氰酸酯组分(A)、所述异氰酸酯反应性组分(B)和所述催化剂(D)的总重量计，所述表面活性剂(E)的含量为10wt％或更少。
10.根据权利要求1或2所述的水性聚氨酯分散体，其中所述扩链剂(F)选自由以下项组成的组：包含至少两个胺基的C2-C16脂肪族多胺、包含至少两个胺基的C4-C15脂环族或芳香族多胺、包含至少两个胺基的C7-C15芳脂族多胺；并且
其中按所述异氰酸酯组分(A)、所述异氰酸酯反应性组分(B)和所述催化剂(D)的总重量计，所述扩链剂(F)的含量为1.0wt％至15wt％。
11.一种用于制备根据权利要求1至10中任一项所述的水性聚氨酯分散体的方法，所述方法包括：
(i)在存在所述催化剂(D)的情况下使所述异氰酸酯组分(A)与所述异氰酸酯反应性组分(B)反应以形成预聚物，其中所述异氰酸酯反应性组分(B)包含羟基官能度为3.0以及重均分子量为1,500至12,000g/mol的聚醚多元醇；以及
(ii)在存在所述表面活性剂(E)和水(G)的情况下使所述预聚物与所述亲水性氨基硅氧烷化合物(C)和所述扩链剂(F)反应以形成所述水性聚氨酯分散体。
12.一种合成皮革制品，所述合成皮革制品从上到下包含：
衍生自根据权利要求1至10中任一项所述的水性聚氨酯分散体的聚氨酯皮膜；
衍生自双组分PU复合组合物的基层；以及
可选的背衬基材，其中所述聚氨酯皮膜与所述基层的一侧直接接触，并且所述背衬基材在存在时与所述基层的相对侧直接接触。
13.一种用于制备根据权利要求12所述的合成皮革制品的方法，所述方法包括：
a)提供根据权利要求1至10中任一项所述的水性聚氨酯分散体；
b)用所述水性聚氨酯分散体形成所述聚氨酯皮膜；
c)将所述双组分PU复合组合物施加到所述聚氨酯皮膜的一侧上以形成所述基层；以及
d)可选地将所述背衬基材施加到所述基层的与所述聚氨酯皮膜相对的一侧上。
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