CN111212728A - 包括热塑性聚氨酯薄膜层的复合材料层压板 - Google Patents

包括热塑性聚氨酯薄膜层的复合材料层压板 Download PDF

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Publication number
CN111212728A
CN111212728A CN201880061643.3A CN201880061643A CN111212728A CN 111212728 A CN111212728 A CN 111212728A CN 201880061643 A CN201880061643 A CN 201880061643A CN 111212728 A CN111212728 A CN 111212728A
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thermoplastic polyurethane
article
prepreg
layer
film
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CN201880061643.3A
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Inventor
S·尼斯塔拉
J·J·小翁托西克
G·S·奈斯勒罗德
J·奇特拉诺三世
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Lubrizol Advanced Materials Inc
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Lubrizol Advanced Materials Inc
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Priority to CN202210949159.2A priority Critical patent/CN115302916A/zh
Publication of CN111212728A publication Critical patent/CN111212728A/zh
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Abstract

一种复合材料层压板结构包括一个或多个预浸料层和处于所述一个或多个预浸料的表面上的热塑性聚氨酯薄膜层。还提供了一种制造包括热塑性聚氨酯薄膜的复合材料层压板结构的方法。

Description

包括热塑性聚氨酯薄膜层的复合材料层压板
技术领域
本发明涉及包括热塑性聚氨酯薄膜层的复合材料层压板和制造这类物品的方法。物品包含一个或多个含有纤维的预浸料层，所述预浸料层具有与表面粘结的热塑性聚氨酯薄膜。本发明的结构和方法消除了将涂料施用在预浸料上，以赋予如颜色、耐UV性、耐磨性等性能的需要。
背景技术
复合材料层压板结构是由堆积的预浸料片材制成。层压板结构通常在外表面上涂覆有一个或多个涂料层，以便提供特定的性能，如耐水性、耐溶剂性或耐UV性、耐候性、耐磨性和/或耐腐蚀性。涂料还可以根据应用为层压板提供装饰。涂料的制备和其在复合材料层压板结构上的施用可能是一个耗时且昂贵的工艺。此外，在一些情况下，涂料缺乏耐久性，并且必须定期重新施用或层压板必须进行更换。
因此，需要提供一种耐用的复合材料层压板结构和制造具有所需和有益性能的复合材料层压板结构的方法。
发明内容
本发明提供了一种具有改善表面性能的复合材料层压板和制造该复合材料层压板的方法。该复合材料层压板包含一个或多个含有纤维的预浸料层和一个热塑性聚氨酯薄膜层。预浸料层包含这类已经用树脂(热塑性树脂或热固性树脂之一)浸渍的纤维基材。该预浸料层可以包括单向纤维、编织纤维或非编织织物或其组合。将热塑性薄膜层粘附至该预浸料层的外表面。除预浸料树脂和热塑性聚氨酯层外，本发明不需要其他附加的粘合剂材料。
附图说明
图1示出了制造复合材料层压板结构的一个现有技术工艺。
图2示出了根据本发明一个实施例的制造复合材料层压板结构的工艺。
图3示出了制造复合材料层压板结构的第二现有技术工艺。
图4示出了根据本发明另一个实施例的制造复合材料层压板结构的工艺。
具体实施方式
本发明包含由一个或多个含有纤维的预浸料层和热塑性聚氨酯薄膜层制成的复合材料层压板结构。下面将更详细地描述复合材料层压板结构的每层和制造复合材料层压板结构的方法。
含有纤维的预浸料
如本文所用，术语“预浸料”是指用树脂浸渍的纤维片材。该预浸料包括纤维基材，其可以选自单向纤维、由编织纤维制成的织物或非编织织物。用于该纤维的材料(或制成纤维的细丝)可以选自本领域技术人员已知的任何材料，包括但不限于碳、石墨纤维、玻璃、矿物或甚至聚合物(如由聚烯烃、聚乙烯、聚丙烯、芳纶、聚苯唑、聚氨酯、聚乙烯醇、聚丙烯腈、液晶共聚酯、聚酰胺、聚酯或其组合)。
为了形成预浸料片材，所选材料的单个或成束细丝形成的连续纤维可以进行线性取向，以形成单向纤维片材，或细丝或纤维可编织形成编织片材，这是本领域的普通技术人员所熟知的。然后用树脂浸渍纤维片材，以形成预浸料片材。用于形成预浸料的树脂可以包括本领域技术人员已知的任何树脂，例如，环氧树脂、酚醛树脂、双马来酰亚胺、聚酰亚胺、氰酸酯、聚碳酸酯、聚酯、聚苯乙烯、聚醚、丙烯腈、丁二烯、丙烯酸酯、甲基丙烯酸酯、聚缩醛、聚砜、聚氨酯、热塑性聚氨酯及其混合物。有用的树脂可以是热固性树脂或热塑性树脂或其组合。用树脂浸渍纤维片材的方法在本领域是熟知的。在一个实施例中，预浸料中使用的树脂包含环氧树脂，例如热固性环氧树脂。
在一个实施例中，本发明的复合材料层压板中使用的预浸料包含碳纤维。在另一个实施例中，复合材料层压板的预浸料层含有由碳纤维组成的纤维。此实施例中的碳纤维可以用环氧树脂浸渍。在一个实施例中，用热固性环氧树脂浸渍碳纤维。
市售各种类型的预浸料购自氰特(Cytec)和卓尔泰克(Zoltek)(东丽(Toray))等公司，并且其销售名称为
Figure BDA0002421377590000031
的预浸料、
Figure BDA0002421377590000032
的预浸料、
Figure BDA0002421377590000033
的预浸料、
Figure BDA0002421377590000034
的预浸料、
Figure BDA0002421377590000035
的预浸料、
Figure BDA0002421377590000036
技术、BPS–主体面板系统(Body PanelSystems)的预浸料和
Figure BDA0002421377590000037
的预浸料。
热塑性聚氨酯薄膜
本发明的复合材料层压板包括热塑性聚氨酯薄膜层。该热塑性聚氨酯(TPU)通过聚异氰酸酯、多元醇中间体和任选的扩链剂组分反应而获得。在此反应中，必要时使用催化剂。
本领域中技术人员已知的任何聚异氰酸酯均可以用于制造本发明中有用的TPU组合物。在一些实施例中，聚异氰酸酯组分包括一种或多种二异氰酸酯，其可以选自芳香族二异氰酸酯或脂肪族二异氰酸酯或其组合。有用的聚异氰酸酯实例包括但不限于芳香族二异氰酸酯(如4,4'-亚甲基双(苯基异氰酸酯)(MDI)、间二甲苯二异氰酸酯(XDI)、亚苯基-1,4-二异氰酸酯、3,3'-二甲基-4,4'-亚联苯二异氰酸酯(TODI)、1,5-萘二异氰酸酯(NDI)和甲苯二异氰酸酯(TDI))；以及脂肪族二异氰酸酯(如异佛尔酮二异氰酸酯(IPDI)、1,6-六亚甲基二异氰酸酯(HDI)、1,4-环己基二异氰酸酯(CHDI)、癸烷-1,10-二异氰酸酯、赖氨酸二异氰酸酯(LDI)、1,4-丁烷二异氰酸酯(BDI)、五亚甲基二异氰酸酯(PDI)和二环己基甲烷-4,4'-二异氰酸酯(H12MDI))。可以使用两种或更多种聚异氰酸酯的混合物。
如本领域技术人员所理解的，本发明中用于制造有用TPU薄膜的异氰酸酯将取决于最终复合材料层压板结构的所需性能。
本发明中有用的TPU组合物也是使用多元醇中间体组分制成的。多元醇中间体包括聚醚多元醇、聚酯多元醇、聚碳酸酯多元醇、聚硅氧烷多元醇及其组合。
合适的羟基封端聚酯中间体包括线性聚酯，其具有约300至约10000、约400至约5000或约500至约4000的数均分子量(Mn)。通过测定末端官能团测定分子量，并且其是与数均分子量相关。聚酯中间体可以通过以下来生成：(1)一个或多个二醇与一个或多个二羧酸或酸酐的酯化反应或(2)酯交换反应，即一个或多个二醇与二羧酸酯的反应。通常超过一个二醇/酸摩尔比的摩尔比是优选的，以获得具有优势末端羟基的线性链。合适的聚酯中间体还包括各种内酯，如聚己内酯，其通常由ε-己内酯和双官能引发剂(如二乙二醇)制成。所需聚酯的二羧酸可以是脂肪族的二羧酸、脂环族的二羧酸、芳香族的二羧酸或其组合。可以单独使用或以混合物使用的合适二羧酸通常具有4至15的总碳原子，并且包括：琥珀酸、戊二酸、己二酸、庚二酸、辛二酸、壬二酸、癸二酸、十二烷二酸、间苯二甲酸、对苯二甲酸、环己烷二羧酸等。也可以使用上述二羧酸的酸酐，如邻苯二甲酸酐、四氢邻苯二甲酸酐等。己二酸是优选的酸。反应形成理想聚酯中间体的二醇可以是脂肪族的二醇、芳香族的二醇或其组合，其包括上述扩链剂段中的任何二醇，并且具有2至20或2至12的总碳原子。合适的实例包括乙二醇、1,2-丙二醇、1,3-丙二醇、1,3-丁二醇、1,4-丁二醇、1,5-戊二醇、1,6-己二醇、2,2-二甲基-1,3-丙二醇、1,4-环己烷二甲醇、十亚甲基乙二醇、十二亚甲基乙二醇及其混合物。
在一些实施例中，二聚体脂肪酸可以用于制备聚酯多元醇，该聚酯多元醇可以用于制造本发明中有用的TPU组合物。可以用于制备聚酯多元醇的二聚体脂肪酸的实例包括购自Croda市售的PriplastTM聚酯二醇/多元醇和购自Oleon市售的
Figure BDA0002421377590000041
聚酯二醇。
该多元醇组分还可以包含一个或多个聚己内酯聚酯多元醇。本文所述技术中有用的聚己内酯聚酯多元醇包括源自己内酯单体的聚酯二醇。通过伯羟基封端该聚己内酯聚酯多元醇。合适的聚己内酯聚酯多元醇可以由ε-己内酯和双官能引发剂(如二甘醇、1,4-丁二醇或本文列出的任何其他二醇(glycol)和/或二醇(diol))制成。在一些实施例中，该聚己内酯聚酯多元醇是源自己内酯单体的线性聚酯二醇。
有用的实例包括CAPATM2202A(2,000数均分子量(Mn)的线性聚酯二醇)和CAPATM2302A(3,000Mn的线性聚酯二醇)，这两种物质均购自Perstorp Polyols公司。这些材料也可以被描述为2-氧杂环庚酮和1,4-丁二醇的聚合物。
聚己内酯聚酯多元醇可以由2-氧杂环庚酮和二醇制成，其中二醇可以是1,4-丁二醇、二乙二醇、单乙二醇、1,6-己二醇、2,2-二甲基-1,3-丙二醇或其任何组合。在一些实施例中，用于制备聚己内酯聚酯多元醇的二醇是线性的。在一些实施例中，聚己内酯聚酯多元醇由1,4-丁二醇制成。在一些实施例中，聚己内酯聚酯多元醇具有300至10000，或400至5000，或400至4000，或甚至1000至4000的数均分子量。
在制造本发明TPU组合物中有用的羟基封端聚醚中间体包括源自二醇或多元醇(其具有2至15的总碳原子)的聚醚多元醇，在一些实施例中，与包含环氧烷烃(通常为环氧乙烷或环氧丙烷或其混合物)的醚反应的烷基二醇或二醇，该烷基二醇或二醇具有2至6个碳原子。例如，可以先将丙二醇与环氧丙烷反应，再与环氧乙烷反应，生成羟基官能团聚醚。环氧乙烷产生的伯羟基比仲羟基反应性更强，并因此是优选的。市售聚醚多元醇包括聚(乙二醇)(包含与乙二醇反应的环氧乙烷)、聚(丙二醇)(包含与丙二醇反应的环氧丙烷)、聚(四亚甲基醚乙二醇)(包含与四氢呋喃反应的水，也可以被描述为聚合四氢呋喃，且通常被称为PTMEG)。合适的聚醚多元醇还包括环氧烷烃的聚酰胺加合物，并且可以包括，例如，包含乙二胺和环氧丙烷反应产物的乙二胺加合物，包含二乙烯三胺与环氧丙烷反应产物的二乙烯三胺加合物，和类似的聚酰胺类聚醚多元醇。在所述组合物中也可以使用共聚醚。典型的共聚醚包括THF和环氧乙烷或THF和环氧丙烷的反应产物。这些可以购自BASF，如嵌段共聚物
Figure BDA0002421377590000051
B和无规共聚物
Figure BDA0002421377590000052
R。各种聚醚中间体通常具有通过测定末端官能团确定的数均分子量(Mn)，其平均分子量大于约500，如约500至约10,000、约500至约5,000或约700至约3000。在一些实施例中，该聚醚中间体包括两种或更多种不同分子量聚醚的共混物，如2,000Mn和1,000Mn的PTMEG的共混物。
在制备本发明TPU组合物中有用的羟基封端聚碳酸酯包括通过二醇与碳酸酯反应制备的那些聚碳酸酯。美国专利第4,131,731号因其公开羟基封端聚碳酸酯及其制备物，通过引用并入于此。这类聚碳酸酯是线性的，并且具有基本不含其他末端基团的末端羟基。基本的反应物是二醇和碳酸酯。合适的二醇选自含有4至40个，和或甚至4至12个碳原子的脂环族和脂肪族二醇，以及每个分子中含有2至20个烷氧基和每个烷氧基含有2至4个碳原子的聚氧化亚烷基二醇。合适的二醇包括含有4至12个碳原子的脂肪二醇(如1,4-丁二醇、1,5-戊二醇、新戊二醇、1,6-己二醇、2,2,4-三甲基-1,6-己二醇、1,10-癸二醇、氢化二亚油酸乙二醇、氢化二油酸乙二醇、3-甲基-1,5-戊二醇)；和脂环族二醇(如1,3-环己二醇、1,4-二甲基环己烷、1,4-环己二醇-、1,3-二甲基环己烷-、1,4-内亚甲基-2-羟基-5-羟甲基环己烷和聚亚烷基二醇)。反应中使用的二醇可以是单一二醇或二醇混合物，这取决于成品中所需的性能。羟基封端的聚碳酸酯中间体通常是本领域和文献中已知的那些中间体。合适的碳酸酯选自5至7元环构成的碳酸亚烃酯。本文使用的合适碳酸酯包括碳酸乙烯酯、碳酸三亚甲基酯、碳酸四亚甲基酯、碳酸-1,2-丙烯酯、碳酸-1,2-丁烯酯、碳酸-2,3-丁烯酯、碳酸-1,2-乙烯酯、碳酸-1,3-戊烯酯、碳酸-1,4-戊烯酯、碳酸-2,3-戊烯酯和碳酸-2,4-戊烯酯。此外，本文合适的是碳酸二烷基酯、碳酸脂环族酯和碳酸二芳基酯。碳酸二烷基酯可以在每个烷基中含有2至5个碳原子，并且其具体实例是碳酸二乙酯和碳酸二丙酯。碳酸脂环族酯，尤其是碳酸双脂环族酯，可以在每个环结构中含有4至7个碳原子，并且可以有1或2个这类结构。当一个基团是脂环族时，另一个基团可以是烷基或芳基。另一方面，如果一个基团是芳基，则另一个可以是烷基或脂环族。合适的碳酸二芳基酯的实例是碳酸二苯酯、碳酸二甲苯酯和碳酸二萘酯，其可以在每个芳基中含有6至20个碳原子。
可以在本发明TPU组合物中使用的聚硅氧烷多元醇包括α-ω-羟基或胺基或羧酸或巯基或环氧基封端的聚硅氧烷。实例包括以羟基或胺基或羧酸或巯基或环氧基封端的聚(二甲基硅氧烷)。在一些实施例中，聚硅氧烷多元醇是羟基封端的聚硅氧烷。在一些实施例中，聚硅氧烷多元醇具有300至5,000或400至3,000范围内的数均分子量。
聚硅氧烷多元醇可以通过聚硅氧烷氢化物与脂肪族多元醇或聚氧烷醇之间的脱氢反应获得，以将醇羟基引入到聚硅氧烷主链上。
在一些实施例中，聚硅氧烷可以由一种或多种具有下式的化合物表示：
Figure BDA0002421377590000071
其中：每个R1和R2独立是1至4个碳原子的烷基、苄基或苯基；每个E是OH或NHR3，其中R3是氢、1至6个碳原子烷基或5至8个碳原子环烷基；每个a和b独立是2至8的整数；c是3至50的整数。在含有氨基的聚硅氧烷中，至少一个E基是NHR3。在含有羟基的聚硅氧烷中，至少一个E基是OH。在一些实施例中，R1和R2均是甲基。
合适的实例包括α,ω-羟丙基封端的聚(二甲基硅氧烷)和α,ω-氨基丙基封端的聚(二甲基硅氧烷)，这两种材料均是市售材料。进一步的实例包括聚(二甲基硅氧烷)材料与聚(环氧烷烃)的共聚物。
在一些实施例中，多元醇中间体也可以包含遥爪聚酰胺多元醇。合适的聚酰胺低聚物(包括遥爪聚酰胺多元醇)并没有被过度限定，并且包括低分子量聚酰胺低聚物和在骨架结构中包括N-烷基化酰胺基团的遥爪聚酰胺(包括共聚物)。遥爪聚合物是含有两个反应性末端基团的大分子。在本公开的技术中，胺封端的聚酰胺低聚物可以作为多元醇。术语聚酰胺低聚物是指具有两个或更多个酰胺键的低聚物，或者有时会规定酰胺键的数量。聚酰胺低聚物的子集是遥爪聚酰胺。遥爪聚酰胺是具有高百分比或特定百分比的单一化学类型的两个官能团的聚酰胺低聚物，例如两个末端胺基(表示伯胺、仲胺或混合物)、两个末端羧基、两个末端羟基(又表示伯羟、仲羟或混合物)或两个末端异氰酸酯基(表示脂肪族、芳香族或混合物)。满足遥爪定义的双官能百分比范围包括至少70、80、90或95摩尔百分比的双官能低聚物，而不是较高或较低的官能。反应性胺封端的遥爪聚酰胺是遥爪聚酰胺低聚物，其中末端基团均是胺类型(伯胺或仲胺及其混合物，即不包括叔胺基团)。
在一个实施例中，遥爪低聚物或遥爪聚酰胺将具有通过Brookfield圆盘粘度计测量的粘度，该圆盘在70℃下小于100,000cps，在70℃下小于15,000或10,000cps，在60或50℃下小于100,000cps，在60℃下小于15,000或10,000cps；或在50℃下小于15,000或10,000cps的5rpm的转速旋转。这些粘度是无溶剂或增塑剂的纯遥爪预聚物或聚酰胺低聚物的那些粘度。在一些实施例中，可以使用溶剂稀释遥爪聚酰胺以达到这些范围内的粘度。
在一些实施例中，聚酰胺低聚物是分子量低于20,000g/摩尔的物质，例如，通常低于10,000、5,000、2,500或2,000g/摩尔，其在每个低聚物中具有两个或更多个酰胺键。遥爪聚酰胺的分子量优选与聚酰胺低聚物相同。多个聚酰胺低聚物或遥爪聚酰胺可以用缩合反应连接以形成一般大于100,000g/摩尔的聚合物。
通常，通过羧酸基与胺基的反应或内酰胺的开环聚合形成酰胺键，例如，其中环状结构中的酰胺键转化为聚合物中的酰胺键。在一个实施例中，单体胺基的大部分是仲胺基或内酰胺的氮是叔酰胺基。当胺基与羧酸反应形成酰胺时，仲胺基形成叔酰胺基。出于此公开的目的，酰胺的羰基(例如在内酰胺中)将被视为源自羧酸基。内酰胺的酰胺键由氨基羧酸的羧基与相同氨基羧酸的胺基反应来形成。在一个实施例中，希望用于制造聚酰胺的单体中有小于20、10或5摩尔百分比的单体以在3个或更多的酰胺键聚合中具有官能性。
如果用于形成这些键的额外单体有助于聚合物的预期用途，则此公开中的聚酰胺低聚物和遥爪聚酰胺可以含有少量酯键、醚键、氨基甲酸乙酯键、尿素键等。
如前指出，许多酰胺形成单体在每个重复单元中平均形成一个酰胺键。这些包括当彼此反应时的二酸和二胺，氨基羧酸和内酰胺。当这些单体与同一组中的其他单体反应时，在形成的重复单元的两端也形成酰胺键。因此，将使用酰胺键百分比和酰胺形成单体重复单元的摩尔百分比和重量百分比。酰胺形成单体将用于指在正常酰胺形成缩合连接反应中，在每个重复单元中平均形成一个酰胺键的单体。
在一个实施例中，含有杂原子的连接烃类键的键总数的至少10摩尔百分比，或至少25、45或50，和或甚至至少60、70、80、90或95摩尔百分比被表征是酰胺键。杂原子键是如酰胺、酯、氨基甲酸乙酯、尿素、醚键等的键，其中杂原子连接低聚物或聚合物的两部分，所述低聚物或聚合物的两部分通常被表征是烃(或具有碳碳键，如烃键)。随着聚酰胺中酰胺键数量的增加，聚酰胺中酰胺形成单体的重复单元数量增加。在一个实施例中，至少25wt％，或至少30、40、50，甚至至少60、70、80、90或95wt％的聚酰胺低聚物或遥爪聚酰胺是源自酰胺形成单体的重复单元，也被认定为在重复单元两端形成酰胺键的单体。这类单体包括内酰胺、氨基羧酸、二羧酸和二胺。在一个实施例中，聚酰胺低聚物或遥爪聚胺中至少50、65、75、76、80、90或95摩尔百分比的酰胺键是叔酰胺键。
使用以下等式计算酰胺键总数中叔酰胺键的百分比：
Figure BDA0002421377590000101
其中：n是单体的数量；指数i指某种单体；w叔N是在聚合过程中形成或作为叔酰胺键一部分的单体中的平均氮原子数，(注：形成胺的末端基团在聚合过程中不会形成酰胺基，其数量被排除在w叔N外)；w总N是在聚合过程中形成或作为叔酰胺键一部分的单体中的平均氮原子数(注：形成胺的末端基团在聚合过程中不会形成酰胺基，其数量被排除在w总N外)；并且ni是具有指数i的单体的摩尔数。
通过以下等式计算所有含杂原子键(连接碳氢化合物键)总数中酰胺键的百分比：
Figure BDA0002421377590000102
其中：w总S是聚酰胺聚合过程中，通过与含羧酸单体反应，单体中含杂原子键(连接烃键)的平均数与该单体形成的含杂原子键(连接烃键)的数之和；并且所有其他变量如上定义。本文中使用的术语“烃键”只是重复单元中由连续碳碳键(即，无氮或氧等的杂原子)形成的每个重复单元的烃类部分。此烃类部分将是环氧乙烷或环氧丙烷的乙烯或丙烯部分；十二烷基内酰胺的十一烷基、乙二胺的乙烯基和己二酸的(CH2)4(或丁烯)基。
在一些实施例中，酰胺或叔酰胺形成单体包括二羧酸、二胺、氨基羧酸和内酰胺。合适的二羧酸是指二羧酸的亚烷基部分是2至36个碳原子、更优选地4至36个碳原子的环状、直链或支链(任选地包括芳香基团)亚烷基，任选地每3或10个二酸碳原子最多包括1个杂原子(二酸将比亚烷基部分多包括2个碳原子)。这些包括二聚体脂肪酸、氢化二聚体酸、癸二酸等。
合适的二胺包括具有多达60个碳原子的那些二胺，任选地每3或10个二胺碳原子包括一个杂原子(两个氮原子除外)，和任选地包括各种环状、芳香或杂环基团，前提是其中一个或两个胺基是仲胺。
这类二胺包括购自Albermarle的EthacureTM 90(推测是N,N'-双(1,2,2-三甲基丙基)-1,6-己二胺)；购自Dorf Ketal的ClearlinkTM 1000，或购自Huntsman的JefflinkTM754；N-甲基氨基乙醇；二羟基封端、羟基和胺基封端或二胺基封端的聚(亚烷基氧化物)，其中，亚烷基具有2至4个碳原子，并且具有约40或100至2,000的分子量；N,N'-二异丙基-1,6-己二胺；N,N'-二(仲丁基)苯二胺；哌嗪；高哌嗪；和甲基哌嗪。
合适的内酰胺包括4至12个碳原子的直链或支链亚烷基段，使得内酰胺氮上无取代基的环状结构具有5至13的碳原子总数(当其包括羰基时)，并且内酰胺氮上的取代基(如果内酰胺是叔酰胺)是1至8个碳原子的烷基，更理想的是1至4个碳原子的烷基。十二烷基内酰胺、烷基取代十二烷基内酰胺、己内酰胺、烷基取代己内酰胺和其他具有较大亚烷基的内酰胺是优选内酰胺，因为它们提供具有较低Tg值的重复单元。氨基羧酸与内酰胺具有相同数量的碳原子。在一些实施例中，氨基羧酸的胺基和羧酸基之间的直链或支链的亚烷基中的碳原子数是4至12，并且胺基(如果是仲胺基)的氮上的取代基是具有1至8个碳原子或1或2至4个碳原子的烷基。
在一个实施例中，理想地，所述聚酰胺低聚物或遥爪聚酰胺的至少50wt％，或至少60wt％、70wt、80wt％或90wt％包含由如下重复单元结构的二酸和二胺构成的重复单元：
Figure BDA0002421377590000111
其中：Ra是二羧酸的亚烷基部分，并且是2至36个碳原子、更优选地4至36个碳原子的环状、直链或支链(任选地包括芳香基)亚烷基，任选地每3或10个二酸碳原子最多包括1个杂原子(二酸将比亚烷基部分多包括2个碳原子)；并且Rb是2至36或60个碳原子并且更优选2或4至12个碳原子的直接连接或直链或支链(任选是或包括环、杂环或芳香部分)的亚烷基(任选地每10个碳原子含有最多1或3个杂原子)，并且Rc和Rd各自是1至8个碳原子，更优选地1或2至4个碳原子的直链或支链烷基，或Rc和Rd连接在一起以形成1至8个碳原子的单个直链或支链的亚烷基，或任选地Rc和Rd中的一个在碳原子上连接至Rb，更理想的是Rc和Rd是1或2至4个碳原子的烷基。
在一个实施例中，理想地，所述聚酰胺低聚物或遥爪聚酰胺的至少50wt％，或至少60wt％、70wt、80wt％或90wt％包含以下结构的内酰胺或氨基羧酸的重复单元：
Figure BDA0002421377590000121
在源于内酰胺或氨基羧酸的低聚物中，重复单元可以在不同取向上，这取决于引发剂的类型，其中每个Re独立地是4至12个碳原子的直链或支链亚烷基，并且每个Rf独立地是1至8个碳原子的直链或支链烷基，更理想的是1或2至4个碳原子的直链或支链烷基。
在一些实施例中，遥爪聚酰胺多元醇包括具有以下的那些：(i)重复单元，其源于通过重复单元与选自羧基或伯胺或仲胺的官能末端基团之间的键而连接的聚合单体，其中至少70摩尔百分比的遥爪聚酰胺恰好具有从由氨基或羧基末端基团组成的群组中选择的相同官能类型的两个官能末端基团；(ii)聚酰胺段，包含至少两个以胺与羧基反应为特征的酰胺键，并且所述聚酰胺段包含选自内酰胺、氨基羧酸、二羧酸和二胺中的两个或更多个单体聚合得到的重复单元；(iii)其中含有杂原子的连接烃类键的键总数的至少10百分比被表征是酰胺键；和(iv)其中至少25百分比的酰胺键被表征是叔酰胺键。
本发明中有用的TPU组合物可以任选地使用扩链剂组分来制成。扩链剂包括二醇、二胺及其组合。
合适的扩链剂包括相对较小的多羟基化合物，例如具有2至20或2至12或2至10个碳原子的较低脂肪族或短链二醇。合适的实例包括乙二醇、二甘醇、丙二醇、二丙二醇、1,4-丁二醇(BDO)、1,6-己二醇(HDO)、1,3-丁二醇、1,5-戊二醇、新戊二醇、十二烷二醇、1,4-环己烷二甲醇(CHDM)、2,2-双[4-(2-羟乙氧基)苯基]丙烷(HEPP)、六亚甲基二醇、庚二醇、壬二醇、十二烷二醇、3-甲基-1,5-戊二醇、乙二胺、丁二胺、六亚甲基二胺和羟乙基间苯二酚(HER)等以及其混合物。在一些实施例中，扩链剂包括BDO、HDO、3-甲基-1,5-戊二醇或其组合。在一些实施例中，扩链剂包括BDO。可以使用其他二醇，如芳香族二醇，但在一些实施例中，本文所述的TPU基本上不含或甚至完全不含这类材料。
为了制备本发明中有用的TPU组合物，三种反应物(多元醇中间体、二异氰酸酯和扩链剂)可以在一起反应。任何已知的使这三种反应物反应的工艺均可以用于制造TPU。在一个实施例中，工艺是一种所谓的“一次性”工艺，其中将所有三种反应物加入挤出机反应器中并进行反应。二异氰酸酯的当量重量与含羟基组分(即多元醇中间体和扩链剂二醇)的总当量重量的比可以是约0.95至约1.10，或约0.96至约1.02，和甚至约0.97至约1.005。使用氨基甲酸乙酯催化剂的反应温度可以是约175℃至约245℃，并且在另一个实施例中其是180℃至220℃。
在另一个实施例中，也可以使用预聚合物工艺制备TPU。在预聚合物路线中，多元醇中间体通常与当量过量的一种或多种二异氰酸酯反应以形成预聚合物溶液，所述预聚合物溶液中具有游离或未反应的二异氰酸酯。反应通常在存在合适氨基甲酸乙酯催化剂的情况下于约80℃至约220℃或约150℃至约200℃温度下进行。随后，加入与异氰酸酯末端基团以及任何游离或未反应的二异氰酸酯化合物大致相等当量的如上所述的扩链剂。因此，总二异氰酸酯与多元醇中间体和扩链剂总当量的总体当量比是约0.95至约1.10，或约0.96至约1.02，并且甚至约0.97至约1.05。扩链反应温度一般是约180至约250℃或约200至约240℃。通常，预聚合物路线可以在包括挤出机在内的任何常规装置中进行。在这类实施例中，多元醇中间体在挤出机第一部分中与当量过量二异氰酸酯反应，以形成预聚物溶液，随后在下游部分添加扩链剂，并与该预聚合物溶液反应。可以使用任何常规的挤出机，包括配备有长度直径比为至少20的并且在一些实施例中至少25的屏障螺杆。
在一个实施例中，在单或双螺杆挤出机上混合成分，所述挤出机在其进料端和模具端之间具有多个加热区和多个进料口。可以在一个或多个进料口处添加成分，并且可以将离开挤出机模具端的所得TPU组合物制成颗粒。
根据常规程序和方法制备各种聚氨酯，并且因为如上所述，通常可以使用任何类型的聚氨酯，不同量的其特定组分、不同的反应物比例、处理温度、催化剂的量、聚合设备(如各种类型的挤出机)等通常都是常规的，并且是在本领域和文献所熟知的。
对于本发明，在一些实施例中，TPU可以通过在“一次性”聚合工艺中将组分在一起反应来制成，其中所有组分(包括反应物)同时或基本上同时添加到加热的挤出机中，并反应形成TPU。在其他实施例中，TPU可以通过以下来制成：首先将聚异氰酸酯组分与多元醇组分的一些部分反应形成预聚合物，然后通过将预聚合物与剩余反应物反应来完成反应，得到TPU。
聚合反应中可以存在一种或多种聚合催化剂。通常，任何传统的催化剂都可以用来使二异氰酸酯与多元醇中间体或扩链剂反应。特别加速二异氰酸酯的NCO基与多元醇和扩链剂的羟基之间反应的适当催化剂的实例是现有技术中已知的常规叔胺，例如三乙胺、二甲基环己胺、N-甲基吗啉、N,N′-二甲基哌嗪、2-(二甲基氨基乙氧基)乙醇、二氮杂双环[2.2.2]辛烷等，并且也特别包括有机金属化合物，如钛酯、铁化合物(例如乙酰丙酮铁)、锡化合物(例如二乙酸亚锡、二辛酸亚锡、二月桂酸亚锡)或脂肪族羧酸的二烷基锡盐(例如二乙酸二丁基锡，二月桂酸二丁基锡等)，或铋化合物(如辛酸铋，月桂酸铋等)。催化剂的通常用量是每100重量份多羟基化合物(b)0.0001至0.1重量份。
各种类型的任选组分可以存在于聚合反应过程中，和/或掺入上述TPU弹性体中，以改善加工性能和其他性能。这些添加剂包括但不限于抗氧化剂(如酚类、有机亚磷酸盐、膦和膦酸盐、受阻胺、有机胺、有机硫化合物、内酯和羟胺化合物)、杀菌剂、杀真菌剂、抗菌剂、增容剂、电耗散或抗静电添加剂、填充剂和增强剂(如二氧化钛、氧化铝、粘土和炭黑)、阻燃剂(如磷酸盐、卤化材料和烷基苯磺酸盐的金属盐)、冲击改性剂(如甲基丙烯酸酯-丁二烯-苯乙烯(“MBS”)和甲基丙烯酸甲酯-丁基丙烯酸酯(“MBA”))、脱模剂(如蜡、脂肪和油)、颜料和着色剂、增塑剂、聚合物、流变改性剂(如单胺、聚酰胺蜡、硅酮和聚硅氧烷)、滑移添加剂(如石蜡蜡、碳氢化合物聚烯烃和/或氟化聚烯烃)和UV稳定剂(其可以是受阻胺光稳定剂(HALS)和/或UV光吸收剂(UVA)类型)。其他添加剂可以用于提高TPU组合物或共混产品的性能。上述所有添加剂均可以按这些物质的常用有效量来使用。
这些额外的添加剂可以掺入到TPU树脂制备的组分中或TPU树脂制备的反应混合物中，或在制造TPU树脂后。在另一个工艺中，所有材料可以与TPU树脂混合，然后熔化，或者直接掺入TPU树脂的熔体中。添加剂可以由本领域普通技能人员根据需要赋予本发明复合材料层压板所需性能来进行选择。
在本发明的一个实施例中，用于制造复合材料层压板用TPU薄膜的TPU组合物包括选自抗氧化剂、杀菌剂、杀真菌剂、抗菌剂、增容剂、电耗散或抗静电添加剂、填充剂和增强剂、阻燃剂、冲击改性剂、脱模剂(如蜡、脂肪和油)、颜料和着色剂、增塑剂、聚合物、流变改性剂、滑移添加剂和UV稳定剂中的一种或多种添加剂。在一个特定的实施例中，本发明的TPU组合物包括UV稳定剂，特别是一种或多种受阻胺类光稳定剂(HALS)和/或UV光吸收剂(UVA)类型。
热塑性聚氨酯薄膜
本发明的组合物及其任何共混物可以形成单层或多层膜。这些薄膜可以通过本领域已知的任何常规技术形成，包括挤出、共挤出、挤出涂覆、层压、吹塑、热成型和铸造或其任何组合。薄膜可以通过平面薄膜或管状工艺获得，随后可以在薄膜平面内以单轴方向或两个相互垂直的方向进行取向。薄膜的一个或多个层可以在横向和/或纵向方向上以相同或不同的程度进行取向。此取向可以发生在各层放在一起之前或之后。通常，薄膜在机器方向(MD)中以高达15，优选5和7之间的比进行取向，并且在横向方向(TD)中以高达15，优选7和9之间的比进行取向。然而，在另一个实施例中，薄膜在MD和TD方向上的取向程度相同。
本发明中有用的薄膜在厚度上可以变化，例如，1μm至5000μm的厚度，例如，1μm至4000μm，1μm至3000μm，1μm至2000μm，或甚至1μm至1000μm可以是合适的。
在另一个实施例中，可以通过电晕处理、电子束辐照、伽马辐照或微波辐照对多于一层进行改性。在优选的实施例中，通过电晕处理对一个或两个表层进行改性。
现在转到附图，图1和图3说明了制备复合材料层压板结构的现有技术工艺。在图1中，含有单向排列纤维1的预浸料层用于形成层压板结构10。层压板结构10可以包括从1到10(例如1到6)的层或单向纤维预浸料。层压板结构10的表面11通常将含有需要填充剂(如油灰)施用的表面缺陷，随后进行砂纸打磨，以提供可以涂漆的表面。将油灰施用在顶层，并且对油灰层进行打磨2，以得到涂漆准备表面。将底漆层3施用于打磨的油灰层2，然后施用油漆的顶部涂层，以提供所需的装饰效果，从而产生完整的碳层压板结构。图3示出了第二现有技术工艺，所述工艺使用至少一个具有单向纤维14的预浸料和具有编织纤维12的预浸料。这些预浸料层被层压在一起，例如，层压板可以包括1至10个，例如，1至6个具有单向纤维的预浸料层；和1至10个，例如，1至6个具有编织纤维的预浸料层。在图3所示的实例中，在层压板上涂覆UV涂层(coating)16，然后将透明涂层(coat)18施用到层压板上。涂层(coating layer)可以需要额外的处理，如抛光，以提供最终有用的复合材料层压板结构。
图2示出了根据本发明一个实施例的制造复合材料层压板结构的工艺。在此实施例中，提供了含有单向排列纤维的预浸料层1和热塑性聚氨酯(TPU)薄膜5。TPU薄膜5可以是透明的或着色的。复合材料结构可以包括1至10个(例如，1至6个)含单向排列纤维的预浸料层。在一个实施例中，当使用多个含有单向排列纤维的预浸料层时，每个预浸料层可以被放置成使得一层纤维与相邻层中的纤维相互垂直。在预浸料层和TPU薄膜上施用热和/或压力，如热成型或层压工艺，以形成复合材料层压板结构。除预浸料层的树脂和TPU薄膜外，无需其他粘合剂。此层压板结构表面的TPU薄膜5准备好直接涂漆，无需进一步处理，以获得最终有用的复合材料层压板结构。
图4示出了根据本发明另一个实施例的制造复合材料层压板结构的工艺。在此实施例中，提供了含有单向排列纤维14的预浸料层、含有编织纤维12的预浸料层和热塑性聚氨酯(TPU)薄膜15。TPU薄膜15可以透明的或有色的。应用热量和/或压力，例如通过热成型或层压工艺，将各层粘在一起。除预浸料层中的树脂和TPU薄膜外，无需其他粘合剂。
在本文所述的层压板中，例如，在附图中所示的那些层压板中，TPU薄膜层可以包含两个TPU薄膜层。在这类实施例中，TPU薄膜层可以包含第一相对较软的层和第二相对较硬的层。例如，第一层可以具有约55邵氏A至95邵氏A(例如，55邵氏A至90邵氏A)的硬度，而第二层具有约95邵氏A至85邵氏D(例如95邵氏A至60邵氏D)的硬度。在一个实施例中，第一层可以具有约1μm至约250μm(例如1μm至约100μm)的厚度，而第二层具有约100μm至约5000μm(例如，约100μm至约4000μm，或甚至约100μm至约3000μm，或甚至约250μm至约2500μm，或甚至约500μm至约1000μm)的厚度。可以将这两个层与相对较软和较薄层的底层(与预浸料相邻放置)和相对较硬的较厚层的顶层(表面)共挤出。
在图2所示的复合材料层压板的一个实施例中，TPU可以包含TPU组合物，其包含芳香族聚异氰酸酯并且具有60邵氏D或以上的硬度。如上所述，此芳香族TPU组合物将是双层TPU薄膜中的顶(表面)层。此芳香族TPU组合物可以是透明的或有色的。
在图4所示的复合材料层压板的一个实施例中，TPU可以包含TPU组合物，其包含聚己内酯多元醇，其具有80邵氏A至85邵氏D(例如，60邵氏D至80邵氏D)的硬度。如上所述，此聚己内酯基热塑性聚氨酯组合物将是双层TPU薄膜中的顶层。聚己内酯TPU组合物可以是透明的或有色的。
在本发明中用作表面层的有色或着色TPU组合物可以通过已知的方法进行着色，包括通过在TPU组合物中直接添加色素或通过使用可以添加到TPU组合物中而不影响TPU的其他有益性能的有色TPU母料。
可以配制用于制造如图2和图4所示的实施例中的薄膜的TPU组合物，以为复合材料层压板提供各种有益性能，如耐水、耐溶剂、耐UV光、耐候、耐磨损、耐腐蚀以及本领域已知的任何其他有用的性能。在一个实施例中，本发明的复合材料层压板中使用的TPU组合物是透明的或基本上透明的。在其他实施例中，TPU薄膜可以具有添加的颜料或颜色，以为层压板提供装饰表面。这些性能可以直接从TPU层获得，无需对复合材料层压板结构进行额外处理和额外涂层的施用。
为了制造本发明的复合材料层压板，将所需数量的预浸料层堆叠，并将TPU薄膜放置在预浸料层堆叠的上表面。将排列好的层压材料置于容器中，如高压灭菌器或热成型压片机，温度设定是从约100℉升温至约350℉，例如从200℉升温至325℉。在一些实施例中，该工艺可以需要1小时或更长时间才能完成，但其他工艺可以在数分钟内提供复合材料层压板成品。本发明的复合材料层压板可以成型为模具，也可以成型为层压板的片材，然后根据特殊应用将其切割。
根据本发明制造的复合材料层压板结构可以在广泛的应用中找到用途。应用包括目前已知的或将来在各种工业中开发的复合材料层压板结构的任何用途，包括但不限于航空航天应用，例如机身、发动机以及内部和外部部件；能源应用，例如风力机叶片和机架；汽车应用，例如发动机罩、车顶、保险杠、镜子、仪表板、内板以及外部和内部部件；暴露于高压的容器，例如罐和航空公司机身；混凝土结构应用，例如支柱再加固；体育和娱乐应用，例如鞋底、防护设备、滑雪设备、自行车架、安全设备，如头盔或护垫；全地形车辆；海洋应用，如船只或喷气式滑艇；电子应用；以及其他应用。

Claims (35)

1.一种复合层压制品，包含：
(a)一个或多个预浸料片层，其中所述预浸料片层包含用树脂浸渍的纤维；和
(b)热塑性聚氨酯薄膜层，
其中所述预浸料层与所述热塑性聚氨酯薄膜层不使用单独粘合剂组分而粘结在一起。
2.根据权利要求1所述的制品，其中所述热塑性聚氨酯薄膜由热塑性聚氨酯组合物制成，所述组合物包含多元醇组分、聚异氰酸酯组分和任选的扩链剂组分的反应产物。
3.根据权利要求1或2所述的制品，其中所述多元醇组分包含聚酯多元醇。
4.根据权利要求3所述的制品，其中所述聚酯多元醇组分包含聚己内酯聚酯多元醇。
5.根据权利要求1或2所述的制品，其中所述多元醇组分包含聚碳酸酯多元醇。
6.根据权利要求1或2所述的制品，其中所述多元醇组分包含聚醚多元醇。
7.根据权利要求1或2所述的制品，其中所述多元醇组分包含聚硅氧烷多元醇。
8.根据权利要求1或2所述的制品，其中所述多元醇组分包含遥爪聚酰胺多元醇。
9.根据权利要求1至8中任一项所述的制品，其中所述聚异氰酸酯包含芳香族二异氰酸酯。
10.根据权利要求9所述的制品，其中所述芳香族二异氰酸酯包含4,4'-亚甲基双(苯基异氰酸酯)。
11.根据权利要求1至8中任一项所述的制品，其中所述聚异氰酸酯包含脂肪族二异氰酸酯。
12.根据权利要求11所述的制品，其中所述脂肪族二异氰酸酯包含H12MDI、HDI或其混合物。
13.根据权利要求1至12中任一项所述的制品，其中所述热塑性聚氨酯薄膜层含有一种或多种添加剂，所述添加剂选自由以下组成的群组：抗氧化剂，抗微生物剂，杀真菌剂，抗菌剂，增容剂，电耗散或抗静电添加剂，填充剂和增强剂，阻燃剂，冲击改性剂，如蜡、脂肪和油的脱模剂，颜料和着色剂、增塑剂、聚合物、流变改性剂、滑移添加剂和UV稳定剂。
14.根据权利要求1至13中任一项所述的制品，其中所述纤维是由选自以下组成的群组的材料制成：碳、石墨、玻璃、矿物或聚合物。
15.根据权利要求1至14中任一项所述的制品，其中所述纤维是碳纤维。
16.根据权利要求15所述的制品，其中所述预浸料片含有单向碳纤维。
17.根据权利要求15所述的制品，其中所述预浸料片含有编织碳纤维。
18.根据权利要求1至17中任一项所述的制品，其中所述复合层压制品包含含有单向碳纤维的第一预浸料片和含有编织碳纤维的第二预浸料片。
19.根据权利要求1至19中任一项所述的制品，其中所述预浸料片的树脂选自环氧树脂、酚醛树脂、双马来酰亚胺、聚酰亚胺、氰酸酯、聚碳酸酯、聚酯、聚苯乙烯、聚醚、苯乙烯、丙烯腈、丁二烯、丙烯酸酯、甲基丙烯酸酯、聚缩醛、聚砜、聚氨酯、热塑性聚氨酯及其混合物。
20.根据权利要求17所述的制品，其中所述树脂是热固性环氧树脂。
21.一种层压制品，包含：
单向纤维预浸料；
编织纤维预浸料；和
热塑性聚氨酯薄膜，其中所述热塑性聚氨酯薄膜是包含多元醇组分、异氰酸酯组分和任选的扩链剂组分的反应产物的挤塑薄膜，
其中不使用单独粘合剂，将所述热塑性聚氨酯薄膜粘附到所述单向纤维预浸料或所述编织纤维预浸料上。
22.根据权利要求21所述的层压制品，其中所述单向纤维预浸料和所述编织纤维预浸料包含碳纤维。
23.根据权利要求21或22所述的层压制品，其中所述单向纤维预浸料和所述编织纤维预浸料包含环氧树脂。
24.根据权利要求21至23中任一项所述的层压制品，其中所述热塑性聚氨酯薄膜包含两层热塑性聚氨酯薄膜，包含具有55A至95A硬度的底部热塑性聚氨酯层和具有95A至85DD硬度的顶部热塑性聚氨酯层。
25.根据权利要求24所述的层压制品，其中所述顶部热塑性聚氨酯层包含聚己内酯多元醇。
26.根据权利要求24或25所述的层压制品，其中所述底部热塑性聚氨酯层具有1μm至250μm的薄膜厚度，并且所述顶部热塑性聚氨酯层具有250μm至5000μm的薄膜厚度。
27.一种层压制品，包含：
第一单向纤维预浸料；
第二单向纤维预浸料；其中所述第一单向纤维预浸料和所述第二单向纤维预浸料定位成彼此毗连，使得所述第一单向纤维预浸料的纤维与所述第二单向纤维预浸料的纤维垂直；
两层热塑性聚氨酯薄膜，包含具有55A至95A硬度的底部热塑性聚氨酯层和具有95A至85D硬度的顶部热塑性聚氨酯层。
28.根据权利要求27所述的层压制品，其中所述底部热塑性聚氨酯层具有1μm至250μm的薄膜厚度，并且所述顶部热塑性聚氨酯层具有250μm至5000μm的薄膜厚度。
29.根据权利要求27或28所述的层压制品，其中所述顶部热塑性聚氨酯层包含芳香族聚异氰酸酯。
30.一种制造复合层压结构的方法，包含：
提供挤塑薄膜，其中所述薄膜包含热塑性聚氨酯组合物，所述组合物包含多元醇组分、异氰酸酯组分和任选的扩链剂组分的反应产物；
提供至少一个预浸料片；
堆叠所述挤塑薄膜和所述至少一个预浸料片；和
施加热量以将所述挤塑薄膜和所述预浸料片粘结在一起。
31.根据权利要求30所述的方法，其中所述提供至少一个预浸料片的步骤包含：
提供一个或多个单向纤维预浸料。
32.根据权利要求30或31所述的方法，其中所述提供至少一个预浸料片的步骤包含：
提供一个或多个编织纤维预浸料。
33.根据权利要求30至32中任一项所述的方法，其中所述提供挤塑薄膜的步骤包含：
提供两层挤塑薄膜，其中所述两层挤塑薄膜包含具有55A至95A硬度的层和具有95A至85D硬度的顶层。
34.根据权利要求33所述的方法，其中所述底层具有1μm至250μm的薄膜厚度，并且所述顶层具有250μm至5000μm的薄膜厚度。
35.根据权利要求30至34中任一项所述的方法，进一步包含：
将所述堆叠的挤塑薄膜和至少一个预浸料片置于模具和压热器中。
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