CN101939395B - 半互穿聚合物网络聚氨酯/聚脲保护膜 - Google Patents

半互穿聚合物网络聚氨酯/聚脲保护膜 Download PDF

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CN101939395B
CN101939395B CN200980104586.3A CN200980104586A CN101939395B CN 101939395 B CN101939395 B CN 101939395B CN 200980104586 A CN200980104586 A CN 200980104586A CN 101939395 B CN101939395 B CN 101939395B
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莱恩·E·马克斯
杰拉尔德·F·弗莱施哈克尔
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3M Innovative Properties Co
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Abstract

本发明提供一种膜、条带或复合材料部件的外层，其包括：a)至少一个包含交联聚合物的层，所述交联聚合物选自交联的聚氨酯、交联的聚脲和交联混合的聚氨酯/聚脲聚合物；以及在一些实施例中，b)粘合剂层。在一些实施例中，所述层另外包含与所述交联聚合物形成半互穿聚合物网络的非交联聚合物。在一些实施例中，所述非交联聚合物可选自聚氨酯、聚脲和混合的聚氨酯/聚脲聚合物。在一些实施例中，所述交联聚合物可另外包含含丙烯酸酯的组分。

Description

半互穿聚合物网络聚氨酯/聚脲保护膜
与相关申请案的交叉参考
本申请要求于2008年2月8日提交的临时专利申请No.61/027177的优先权。
技术领域
本发明涉及包含半互穿聚合物网络(半IPN)的聚氨酯或聚脲条带和膜及其在表面保护中的用途，包括保护飞行器表面免受水和粒子(如沙和粉尘)所致的腐蚀。
发明内容
简言之，本发明提供一种膜或条带，其包括：a)至少一个包含交联聚合物的层，所述交联聚合物选自交联的聚氨酯、交联的聚脲和交联混合的聚氨酯/聚脲聚合物；和b)粘合剂层。在一些实施例中，所述层另外包含与所述交联聚合物形成半IPN的非交联聚合物。在一些实施例中，所述非交联聚合物可选自聚氨酯、聚脲和混合的聚氨酯/聚脲聚合物。在一些实施例中，所述交联聚合物可另外包含含丙烯酸酯的组分。
另一方面，本发明提供一种包括本文所提供的膜或条带的构造，所述膜或条带通过粘合剂层粘结至复合材料部件或金属部件的表面上。
另一方面，本发明提供一种包括树脂基体和外表面层的复合材料部件，所述外表面层与树脂基体在组成上不同，其中外表面包括至少一个包含交联聚合物的层，所述交联聚合物选自交联的聚氨酯、交联的聚脲和交联混合的聚氨酯/聚脲聚合物。在一些实施例中，所述层另外包含与所述交联聚合物形成半IPN的非交联聚合物。在一些实施例中，所述非交联聚合物可选自聚氨酯、聚脲和混合的聚氨酯/聚脲聚合物。在一些实施例中，所述交联聚合物可另外包含含丙烯酸酯的组分。
附图说明
图1是用于测试耐雨水浸蚀性的装置的示意图，如实例中和公布的美国专利申请No.2008/0209981-A1中所述，该专利申请公布于2008年9月4日。
图2是在如实例所述的测试之前的实例1膜和实例4C膜(比较例)在基材上的照片。
图3是在如实例所述的测试之后的实例1膜和实例4C膜(比较例)在基材上的照片。
具体实施方式
本发明涉及包含半互穿聚合物网络(半IPN)的聚氨酯或聚脲条带和膜及其在表面保护中的用途，包括保护飞行器表面免受水和粒子(如沙和粉尘)所致的腐蚀。还涵盖的是保护在使用时或在制造过程中经受高温的表面(不限于飞行器)的能力。半IPN的交联组分可由在非交联组分之内交联而形成网络的氨基甲酸酯(或脲)丙烯酸酯低聚物组成。非交联组分可以是在化学上与交联组分不同的热塑性聚氨酯/聚脲。
在一些实施例中，本发明中公开的保护条带和膜可用于保护飞行器的表面，包括机翼的前缘、天线罩和直升机旋翼，使之不会因水、沙、粉尘或碎片而损坏。与单独的热塑性聚氨酯相比，本发明的半IPN聚氨酯可提供更好的耐腐蚀性。带有压敏粘合剂的条带提供了一种将膜施加至飞行器上的简单方式，使得可以很容易地进行修复。所述膜单独可以承受热塑性膜不可能承受的温度，使得可以将膜共固化到复合结构中。可以改变聚氨酯/聚脲的交联程度，使膜具有耐溶剂性，或使膜是可用溶剂移除的，但仍然具有高温性能。较低的交联程度还可得到在高温下具有完整性且还具有热成形能力的膜。较高的交联程度可能会抑制热成形的可能性。
本发明的保护膜和条带还具有对在使用时或在制造过程期间受热的非飞行器表面进行保护的实用性。体育用品、汽车、工具、烹调或加热设备以及一般的工业应用是这种膜或条带的潜在应用对象，这些应用中具有高作业温度或使用温度，并且需要膜能承受高温。
将下述参考文献的公开内容以引用的方式并入本文：代理人案卷号63528US002，美国专利申请No.11/837293，提交于2007年8月10日；美国专利No.5,959,775；美国专利No.4,948,859；美国专利No.4,859,742；和美国专利No.4,302,553。
一些实施例包括膜或条带，所述膜或条带包括至少一个包含交联聚合物的层以及粘合剂层，所述交联聚合物选自交联的聚氨酯、交联的聚脲和交联混合的聚氨酯/聚脲聚合物。可以使用任何合适的交联聚氨酯或交联聚脲。合适的聚氨酯可以包括多异氰酸酯与多元醇的聚合物。合适的聚脲可以包括多异氰酸酯与多胺的聚合物。在一些实施例中，交联聚合物可以是衍生自多异氰酸酯与多元醇和多胺的混合物的混合聚氨酯/聚脲聚合物。可以使用任何合适的多异氰酸酯、多元醇或多胺。合适的多异氰酸酯可以包括芳族异氰酸酯、脂族异氰酸酯、多异氰酸酯或它们的组合。合适的芳族异氰酸酯可以包括亚甲基二苯基二异氰酸酯、1，4-亚苯基二异氰酸酯、1，3-亚苯基二异氰酸酯、3，3′-二甲基二苯基甲烷-4，4′-二异氰酸酯、二苯甲烷-2，2′-二异氰酸酯、萘二异氰酸酯、4，4′-联苯二异氰酸酯、1，5-萘二异氰酸酯、2-甲基-1，5-萘二异氰酸酯、2，4-甲苯二异氰酸酯和2，6-甲苯二异氰酸酯以及该两种异构体的混合物、二苯甲烷-2，4′-二异氰酸酯、4-乙基-间-亚苯基二异氰酸酯等，或它们的混合物。合适的脂族异氰酸酯可包括2，4，4-三甲基六亚甲基二异氰酸酯、2，2，4-三甲基六亚甲基二异氰酸酯、1，4-环己烷二异氰酸酯、1，3-环己基二异氰酸酯、三甲基六亚甲基二异氰酸酯、异佛乐酮二异氰酸酯(IPDI)、十亚甲基二异氰酸酯、亚甲基二异氰酸酯、亚甲基-双(4-环己基异氰酸酯)(H12MDI)、二甲基二异氰酸酯、反-1，4-环己烷二异氰酸酯、六亚甲基二异氰酸酯等，或它们的混合物。其它合适的异氰酸酯可以包括多异氰酸酯，包括基于上述物质任一种的那些。合适的多元醇可包括聚酯多元醇、聚己内酯多元醇、聚醚多元醇、羟基封端的聚丁二烯和氢化聚丁二烯多元醇、聚碳酸酯多元醇等，或它们的混合物。合适的多胺可包括JEFFAMINE聚醚胺等，或它们的混合物。此外，可以包含增链剂，该增链剂通常是单体或低分子量双官能化合物。合适的羟基增链剂可以包括乙二醇、二乙二醇、丙二醇、二丙二醇、新戊二醇、1，4-丁二醇和2-甲基-1，3-丙二醇等，或它们的混合物。合适的氨基增链剂可包括1，4-二氨基丁烷、乙二胺、1，2-二氨基丙烷、1，3-二氨基丙烷、1，2-二氨基环己烷、异佛乐酮二胺、仲环脂族二胺、二乙基甲苯二胺等，或它们的混合物。
在一些实施例中，所述交联聚合物可另外包含丙烯酸酯组分。丙烯酸酯组分衍生自任何合适的丙烯酸酯组分前体，该前体是带有可供聚合的丙烯酸酯双键的任何合适的单体、低聚物或聚合物。在一些实施例中，在条带的形成期间，丙烯酸酯组分前体通过电子束或其它辐射交联，从而形成最终存在于成品条带中的丙烯酸酯组分。
在一些实施例中，在丙烯酸酯组分前体交联之前，使丙烯酸酯组分前体共聚至聚氨酯或聚脲中。该类型的合适丙烯酸酯(例如SR495B)包含一个或多个与聚氨酯或聚脲聚合的基团(如醇或胺基团)和一个或多个可供聚合的丙烯酸酯双键。其它合适的物质可包括己内酯丙烯酸酯、羟乙基丙烯酸酯、二季戊四醇五丙烯酸酯等，或它们的混合物。
在一些实施例中，在丙烯酸酯组分前体交联之前，使丙烯酸酯组分前体与聚氨酯或聚脲共混。在该实施例中，聚氨酯或聚脲在最终的条带中与交联的丙烯酸酯组分形成半IPN。形成的半IPN中含丙烯酸酯的组分交联而其它聚氨酯或聚脲未交联。该类型的合适丙烯酸酯包括CN996、CN9893等，包括得自Sartomer的这类丙烯酸酯。该类型的合适丙烯酸酯通常至少部分地可混溶于聚氨酯或聚脲中。
可以通过任何合适的手段使交联聚合物交联，包括辐射交联(如通过电子束、UV、可见光、IR等)或通过制造期间在聚合物中添加交联剂或多官能单体实现的共价交联。多官能单体可包括多异氰酸酯、多元醇、多胺等，或它们的混合物。
所述条带或膜通常是透明或半透明的，但也可以是着色的。所述条带可以具有任意合适的厚度。典型的厚度在0.01mm至3.0mm之间，更典型地在0.01mm至1.0mm之间，更典型地在0.1mm至1.0mm之间，更典型地在0.25mm至1.0mm之间，并且更典型地在0.25mm至0.75mm之间。
可以使用任何合适的粘合剂层。在一个实施例中，所述粘合剂层可以包含丙烯酸类粘合剂。在一个实施例中，所述粘合剂是压敏粘合剂。在一个实施例中，所述粘合剂是结构粘合剂。在一个实施例中，所述粘合剂是二元粘合剂在一个实施例中，所述粘合剂是能量固化粘合剂。在一个实施例中，所述粘合剂是空气固化粘合剂。合适的粘合剂可以包括丙烯酸类树脂、聚氨酯、硅树脂、苯乙烯-丁二烯嵌段共聚物、苯乙烯-异戊二烯嵌段共聚物、环氧树脂、氰基丙烯酸酯、二元氨基甲酸酯等。
条带可通过包括下面实例中所示方法在内的任何合适方法制备。合适的方法可以包括使聚氨酯或聚脲组分与可交联的组分共混、反应性挤出或反应性涂布。
使用纤维增强的树脂基体或纤维增强的塑料(FRP)基体复合层合材料(“复合材料”)已在航空、汽车及其它运输行业的各种应用中被广泛接受，因为它们具有质量轻、高强度和高硬度的性质。将纤维增强的树脂基体复合层合材料应用到工业应用中的最大推动力是重量减轻的有益效果和性能的增强。多种航空部件是由玻璃纤维和碳纤维增强的复合材料制造的，包括飞机机身部分和机翼结构。复合材料被用于制造飞机、风力发电机、汽车、体育用品、家具、公共汽车、卡车、船舶、火车车厢的许多部件，以及用于其它应用当中(在这些应用中，材料的刚性、轻量化或部件的增强是有利的)。最通常的情况是，纤维由碳、玻璃、陶瓷或芳族聚酰胺制成，树脂基体是有机热固性或热塑性材料。这些部件通常是在真空和/或压力条件下制造的，制造时的温度为0℃至180℃，有时高达230℃。在一些实施例中，可以把根据本发明的膜或条带粘附至这种复合材料部件上。
在一些实施例中，可使用根据本发明的膜或条带给用于形成部件的模具加衬里，从而使得经模制工序后所得的部件具有由所述膜或条带构成的外表面。在一些实施例中，这种部件是复合材料部件。可以采用合适的模制工艺，包括聚合物、复合材料、玻璃纤维等的模制。本发明包括具有外层的模制部件，所述外层全部或部分地包括根据本发明的膜或条带。模制部件可以是任何合适的模制材料，包括热塑性聚合物、热固性聚合物、可固化聚合物、复合材料、玻璃纤维、陶瓷、粘土等。
本发明的目的和优点将通过以下实例进一步说明，但在这些实例中列举的具体材料及其量，以及其它的条件和细节不应该被理解成是对本发明的不当限制。
实例
以下实例说明了半IPN聚氨酯条带的制备，并且证明这些条带与类似的热塑性聚氨酯条带相比耐久性改善。制备了两种半IPN聚氨酯条带。
除非另外说明，否则所有的试剂均得自或可得自Aldrich ChemicalCo.(Milwaukee，Wisc.)，或者可通过已知的方法合成。
表1.实例中所用的材料
膜挤出
在58mm戴维斯标准同向旋转双螺杆挤出机上进行膜挤出。它的L/D比为大约84∶1，通过26英寸宽的模头挤出。用在线的电晕处理装置对膜进行电晕处理。
将样品浇铸到粗面纸造模衬片上。造模衬片具有粘附于背面的聚酯条带，用以防止聚氨酯粘住它并在退绕时将纸撕裂。表2示出了样品的组分加料速率。
表2.挤出速率
通过Ktron计重给料机分别供给聚氨酯和颜料。由热的压力容器供给CN9893。压力容器容量15加仑，由不锈钢制成。通过包裹加热套对其进行加热。加热套的温度设置为170℉。用空气将罐体加压到60psi，用针形阀手动控制流速。将罐体放在磅秤上，使得能够连续地监测流速/重量损失。
挤出26″宽和0.024″厚的料卷。每卷收集大约200码。
电子束处理
用电子束照射该聚氨酯卷。由于膜厚度和电子束装置的电压限制(最大260kV)的原因，使样品两次穿过电子束以便从两面照射样品。表3汇总了用于样品的电子束条件。
表3.电子束条件
在电子束暴露之后，样品已成为半IPN聚氨酯，其中丙烯酸酯在热塑性聚氨酯的内部形成了交联网络。为了对此予以验证，将所有样品加热到300℉达30分钟，没有变得有光泽。如果没有形成网络的话，那么膜本应变得有光泽。还通过将一条材料放在热风枪前面对它们全部进行了测试。样品没有融化，表明已经形成了网络。
用粘合剂涂布
用90/10的丙烯酸异辛酯/丙烯酸单体混合物与光引发剂涂布样品，涂层厚度为3密耳(0.076mm)，然后进行UV固化以形成丙烯酸类压敏粘合剂。
雨水浸蚀模拟装置
图1中所示为用于测试耐雨水浸蚀性的装置的示意图。该装置详细地描述在3M公司的专利提交文件“METHOD OF TESTING LIQUIDDROP IMPACT AND APPARATUS”(代理人案卷号62547US002，美国专利申请序列号11/680,784，提交于2007年3月1日)中。
使用0.177口径的气枪(“Drozd Air Gun”，European AmericanArmory Corporation，Cocoa，FL)，以及将1/2英寸直径的聚氯乙烯管作为管筒部分来组装图1的测试装置。通过使用与设定为约60psi的压缩氮气储罐(Oxygen Service Company，St.Paul，MN)连接的粒丸枪推动4.5mm的II级乙酸盐粒料(Engineering Laboratories，Inc，Oakland，NJ)。用通过使用水泵(部件为23609-170，VWR，West Chester，PA)输送的水流注连续地覆盖样品。用CED Millennium测速仪(得自CompetitiveEdge Dynamics LLC(Orefield，Pa))测量粒料的速度。
样品通过这样测试：切下直径为6.1cm并且中间具有直径为2.2cm的孔的圆形物，将其粘附于圆形的304不锈钢板，所述不锈钢板外径为7.6cm并且带有直径为0.35cm的中心孔。在测试前让样品在基材上留置24小时。以3次射击/秒的射击速率进行测试。测试结果示于表4中。
表4.模拟雨水浸蚀测试的结果
  样品   平均速度(ft/s)   失效时的平均射击次数
  实例1膜   361.7   371.3
  实例2膜   363.3   372.3
  比较例3C(PPT 8667)   361.5   245.0
由较高的“失效时的射击次数”显而易见的是，实例1和2的膜显示出比比较例3C的PPT 8667更具有耐久性。实例1和2的膜是半IPN聚氨酯，而比较例3C膜(PPT 8667)是相同厚度的热塑性聚氨酯。
共固化
该实例显示了半IPN聚氨酯能共固化到复合结构中的能力。这能使膜粘附到复合材料当中而不需要用压敏粘合剂。这用半IPN聚氨酯是可行的，因为交联的网络能防止在固化过程期间膜的融化和流动。
将如下程序用于证明在高温下共固化到复合材料当中的能力。将2.5英寸长的铝机翼试样块试件用作模具。将该模具的顶部上放置防粘衬垫。在防粘衬垫的顶部上叠置以0°-90°-0°十字形布置的8层预浸渍料。将预浸渍料层全部切成2.5″×3.5″的方块。在预浸渍料的顶部上放置1.25″×3.5″的不带有粘合剂的实例1膜样品(如先前实例中制备)，与之并列放置标示为例4C的1.25″×3.5″的PPT 8542样品(无粘合剂)。在聚氨酯的顶部放置另一防粘衬垫。把该构造放置在真空工作台上并用橡胶垫覆盖。在该构造上抽吸真空，将橡胶垫吸向复合材料。用十分钟的过程将真空工作台加热至250℉。当工作台达到250℉时，将其在该温度下再保持10分钟。关掉加热并再继续保持真空状态5分钟以协助冷却工作台。此后，移出复合材料并进行检查。
图2和图3是测试前后实例1和例4C膜的照片。随着聚氨酯融化，黑色的比较例4C膜变得有光泽。当真空将橡胶垫向下吸并朝底部挤压聚氨酯时，实例4C的聚氨酯的融化也使它向下流。这在试样块的顶部上留下实例4C膜的薄层和朝向基部的较厚的褶皱膜。实例1膜变得略微更有光泽，但仍然保持其粗面外观它在不融化和不流动的情况下模制成复合体。
在不背离本发明的范围和原理的条件下，本发明的各种修改和更改对本领域技术人员来说将是显而易见的，并且应当理解，本发明不应不当地受限于上文示出的示例性实施例。

Claims (5)

1.一种纤维增强的树脂基体复合材料部件，所述复合材料部件包括树脂基体和外表面层，所述外表面层与所述树脂基体的组成不同，其中所述外表面包括至少一个包含膜或条带的层，所述膜或条带包含交联聚合物，所述交联聚合物选自交联的聚氨酯、交联的聚脲和交联混合的聚氨酯/聚脲聚合物，其中所述外表面层另外包含与所述交联聚合物形成半IPN的非交联聚合物；和其中所述树脂基体是有机热固性或热塑性材料。
2.根据权利要求1所述的部件，其中所述非交联聚合物选自聚氨酯、聚脲和混合的聚氨酯/聚脲聚合物。
3.根据权利要求1所述的部件，其中所述交联聚合物另外包含含丙烯酸酯的组分。
4.根据权利要求1所述的部件，其中所述交联聚合物另外包含含丙烯酸酯的组分。
5.根据权利要求2所述的部件，其中所述交联聚合物另外包含含丙烯酸酯的组分。
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