CN103221208B - 聚酰胺复合结构及其制备方法 - Google Patents
聚酰胺复合结构及其制备方法 Download PDFInfo
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- CN103221208B CN103221208B CN201180052593.0A CN201180052593A CN103221208B CN 103221208 B CN103221208 B CN 103221208B CN 201180052593 A CN201180052593 A CN 201180052593A CN 103221208 B CN103221208 B CN 103221208B
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- Prior art keywords
- polyamide
- resin composition
- group
- composite construction
- fibrous material
- Prior art date
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Abstract
本发明公开了聚酰胺复合结构及其制备方法。本发明所公开的复合结构包括表面并且包含纤维材料,所述表面的至少一部分由表面树脂组合物制成,并且所述纤维材料经基质树脂组合物浸渍。所述表面树脂组合物选自包含以下物质的共混物的聚酰胺组合物:A)具有低于230℃熔点的全脂族聚酰胺,和(B)具有至少250℃熔点的全脂族聚酰胺,并且其中所述基质树脂组合物独立地选自(B)或选自(A)与(B)的共混物。
Description
技术领域
本发明涉及复合结构及其制备方法的领域,具体地,本发明涉及聚酰胺复合结构的领域。
背景技术
为了替换金属部件以减轻重量和降低成本并同时保持相当的或更优的机械性能,开发了基于复合材料的结构,所述复合材料具有包含纤维材料的聚合物基质。随着对此领域关注度的日益增长,已设计了纤维增强的塑性复合结构,原因在于其具有由纤维材料和聚合物基质的组合而产生的优异物理性能,并且这些纤维增强的塑性复合结构已用于多种最终应用中。已开发了多种制造技术来改善聚合物基质对纤维材料的浸渍,从而优化复合结构的性能。
在要求很高的应用中,例如机动车和航空航天应用中的结构部件,由于复合材料具有重量轻、强度高和耐温性的独特组合,因而是所期望的。
可使用热固性树脂或热塑性树脂作为聚合物基质来获得高性能复合结构。基于热塑性的复合结构相对于基于热固性的复合结构表现出若干优点,例如以下事实:它们可通过施加热和压力被后成型或再加工,由于不需要固化步骤而减少了制备复合结构所需的时间,并且增加了回收利用的可能性。实际上,在热塑性塑料的加工期间,不需要热固性树脂耗时的化学交联(固化)反应。在热塑性树脂中,聚酰胺尤其适于制造复合结构。由于热塑性聚酰胺组合物的良好机械性能、耐热性、抗冲击性和耐化学品性,并且人们可方便灵活地将其模制成多种不同复杂度与精细度的制品,因此期望将热塑性聚酰胺组合物用于各种不同的应用中,包括机动车中所用的部件、电气/电子部件、家用电器和家具。
US4,255,219公开了可用于形成复合材料的热塑性片材料。本发明所公开的热塑性片材由聚酰胺6和二元羧酸或其酸酐或酯以及包封于所述层内的至少一个长玻璃纤维增强垫制成。
为了制备整体复合结构并提高聚合物的性能,常常期望将由聚合物制成的一个或多个部件“重叠注塑”到复合结构表面的一部分或全部上以包围或包封所述表面。重叠注塑涉及成型,例如通过将第二聚合物部分直接注塑到所述复合结构的一个或多个表面的至少一部分上以形成两部件的复合结构成型,其中所述两个部件在至少一个界面处彼此粘附。期望用于浸渍纤维材料的聚合物组合物(即基质聚合物组合物)和用于重叠注塑经浸渍的纤维材料的聚合物组合物(即重叠注塑聚合物组合物)彼此粘附良好,具有极好的尺寸稳定性,并在不利条件包括热循环条件下保持它们的机械性能,使得复合结构在操作条件下受到保护并因此具有增加的寿命。
遗憾的是,用于浸渍一个或多个纤维层和重叠注塑一个或多个经浸渍的纤维层的常规热塑性聚酰胺树脂组合物可能在压印、形成或成型期间需要过热(其可导致其表面在外观和功能上不佳),和/或在重叠注塑的聚合物与包含纤维材料的组件表面(即复合结构)之间表现出不良粘附性。不良粘附性可导致在重叠注塑的复合结构的界面处形成裂纹,从而导致机械性能降低、过早老化以及随着使用次数增多和时间流逝而出现与制品分层和劣化相关的问题。
在这种弱粘附性的情况下,所述复合结构与所述重叠注塑性树脂之间的界面将首先断裂,使所述重叠注塑的复合结构比其任何一种组件都更为脆弱。因此,高度期望组件之间的高粘附强度。然而,一旦粘结强度高到足以使所述界面可承受所施加的负荷而不首先断裂,则该结构的更高机械性能是高度期望的,这是对大多数要求很高的应用的需要。在这些大多数要求很高的应用中,较低的机械性能可随着使用次数增多和时间流逝而损害制品的耐久性和安全性。弯曲强度,即在弯曲测试期间由测试样本承受的最大弯曲应力,通常被用作当弯曲时材料支承(或承受、或支撑)负荷的能力的指示。当将树脂组合物重叠注塑到复合结构的至少一部分上时,期望所述结构的高机械性能(诸如弯曲强度)超过所述复合结构与所述重叠注塑性树脂之间的良好粘结强度所能实现的。
存在对于易于在形成、成型或压印中进行处理的热塑性聚酰胺复合结构的需要,所述复合结构表现出良好的机械性能(尤其是弯曲强度)并且其表面的至少一部分允许其表面与包含聚酰胺树脂的重叠注塑性树脂之间的良好粘附性。
发明内容
本文描述了具有表面并且包含纤维材料的复合结构,所述表面的至少一部分由表面树脂组合物制成,并且所述纤维材料选自非织造结构、纺织品、纤维絮片以及它们的组合,所述纤维材料经基质树脂组合物浸渍,其中所述表面树脂组合物选自包含以下物质的共混物的聚酰胺组合物:(A)选自具有低于230℃的熔点的组(I)聚酰胺的一种或多种全脂族聚酰胺,和(B)选自具有至少250℃的熔点的组(II)聚酰胺的一种或多种全脂族聚酰胺,并且其中所述基质树脂组合物独立地选自(B)或独立地选自(A)与(B)的共混物。
本文还描述了用于制备上述复合结构的方法。制备上述复合结构的方法包括以下步骤:i)用基质树脂组合物浸渍纤维材料,其中所述复合结构表面的至少一部分由表面树脂组合物制成。
具体实施方式
本发明的复合结构具有改善的抗冲击性和弯曲强度,并且当由包含热塑性聚酰胺的重叠注塑性树脂组合物制成的部件粘附到所述复合结构表面的至少一部分上时,其允许良好的粘附性。所述复合结构的良好抗冲击性和弯曲强度以及所述复合结构与所述重叠注塑性树脂之间的良好粘附性导致结构随着使用次数增多和时间流逝表现出所述结构的良好抗劣化性和抗分层性。
在本说明书中引用了若干专利和出版物。所有这些专利和出版物的全部公开内容均以引用方式并入本文。
如本文所用,术语“一个/一种”是指一个/一种以及是指至少一个/一种,并且不是必定限制其指示名称为单数的冠词。
如本文所用,术语“约”和“为或为约”旨在表示所述量或数值可为指定值或与指定值接近的某个其它值。所述短语旨在表示,根据本发明,类似的值产生了相同的结果或效果。
如本文所用,关于聚酰胺,术语“熔点”是指根据差示扫描量热法(DSC)在第一次加热扫描中以10℃/min的扫描速率测定的纯树脂的熔点,其中在最大吸热峰处获取所述熔点。在聚合物共混物的熔解行为的典型测量中,可对单一样品进行多于一次的加热扫描,并且第二次和/或此后的扫描可能表现出与第一次扫描不同的熔解行为。该不同的熔解行为可以最大吸热峰的温度变动的形式和/或以熔解峰的加宽(可能具有多于一个峰)而观测到,其可能是在多于一种聚酰胺的情况下的可能的转酰胺的效应。然而,当在本发明的范围内针对组I或组II聚酰胺而选择聚酰胺时,总是使用对单一聚酰胺的第一次加热扫描的熔解吸热峰。如本文所用,扫描速率是每单位时间温度的提高。必须提供充足的能量以维持10℃/min的恒定扫描速率直至达到高于该熔点至少30℃并优选至少50℃的温度。
本发明包含经基质树脂组合物浸渍的纤维材料。复合结构表面的至少一部分由表面树脂组合物制成。基质树脂组合物和表面树脂组合物可相同或不同。
如本文所用,术语“经基质树脂组合物浸渍的纤维材料”是指基质树脂组合物包封并嵌入所述纤维材料,以便形成基本上被基质树脂组合物包围的纤维材料的互穿网状物。出于本文的目的,术语“纤维”是指宏观上均匀的主体,所述主体在垂直于其长度方向的横截面区域上具有高的长宽比。所述纤维横截面可为任何形状,但通常为圆形。纤维材料可为本领域技术人员已知的任何合适的形式,并且优选地选自非织造结构、纺织品、纤维絮片以及它们的组合。非织造结构可选自无规纤维取向的和对齐的纤维结构。无规纤维取向的例子无限制地包括短切和连续的材料,其可为垫、针刺垫或毡的形式。对齐的纤维结构的例子无限制地包括单向纤维股线、双向股线、多向股线、多轴向纺织品。纺织物可选自织造形式、针织品、编织品以及它们的组合。纤维材料可为连续的或不连续的形式。
根据复合结构的最终应用和所需的机械性能,可使用多于一种的纤维材料,具体方式为采用若干相同的纤维材料或不同纤维材料的组合,即本文所述的第一组件可包含一种或多种纤维材料。不同纤维材料的组合的例子是这样的组合,其包含布置成中间层的非织造结构例如平面无规垫,和布置成外层的一种或多种织造的连续纤维材料。此组合可改善第一组件的加工及其同质性,从而得到改善的机械性能。纤维材料可由任何合适的材料或材料混合物制成,前提条件是材料或材料混合物经受基质树脂组合物和表面树脂组合物浸渍期间所用的加工条件。
优选地,纤维材料包括玻璃纤维、碳纤维、芳族聚酰胺纤维、石墨纤维、金属纤维、陶瓷纤维、天然纤维或它们的混合物;更优选地,纤维材料包括玻璃纤维、碳纤维、芳族聚酰胺纤维、天然纤维、或它们的混合物;并且还更优选地,纤维材料包括玻璃纤维、碳纤维和芳族聚酰胺纤维或它们的混合物。所谓天然纤维是指任何植物源或动物源的材料。当使用时,天然纤维优选来源于植物源,如来源于种毛(例如棉花)、茎秆植物(例如大麻、亚麻、竹子;韧皮纤维和芯纤维)、叶片植物(例如剑麻和麻蕉)、农作物纤维(例如谷类秸秆、玉米芯、稻壳和椰纤维)或木质纤维素纤维(例如木材、木质纤维、木屑、纸材以及与木材相关的材料)。如上文所提及,可使用多于一种的纤维材料。可使用由不同纤维制成的纤维材料的组合,例如这样的复合结构:其包括由玻璃纤维或天然纤维制成的一个或多个中间层,以及由碳纤维或玻璃纤维制成的一个或多个表面层。优选地,纤维材料选自织造结构、非织造结构以及它们的组合,其中所述结构由玻璃纤维制成,并且其中所述玻璃纤维为E-玻璃长丝,其具有介于8和30微米之间的直径,并且优选具有介于10至24微米之间的直径。
纤维材料还可包含热塑性材料和上述材料,例如纤维材料可为混纤纱或混编纱的形式或经适于随后加工成织造或非织造形式的热塑性材料制成的粉末浸渍的纤维材料,或用作单向材料的混合物,或经浸渍期间就地聚合的低聚物浸渍的纤维材料。
优选地,所述第一组件中的纤维材料和聚合物材料(即与基质树脂组合物和表面树脂组合物组合的纤维材料)之间的比率为至少30体积%的纤维材料,并且更优选介于40体积%和60体积%之间的纤维材料,所述百分比是基于所述第一组件的总体积计的体积百分比。
基质树脂组合物由热塑性树脂制成,所述热塑性树脂与所述表面树脂组合物相容。表面树脂组合物选自包含以下物质的共混物的聚酰胺组合物:(A)具有低于230℃的熔点的一种或多种全脂族组(I)聚酰胺,和(B)选自具有至少250℃的熔点的组(II)聚酰胺的一种或多种全脂族聚酰胺。基质树脂组合物独立地选自(B)或独立地选自(A)与(B)的共混物。表面树脂组合物和基质树脂组合物可相同或不同。当表面树脂组合物和基质树脂组合物不同并且当基质树脂组合物选自(A)与(B)的共混物时,这是指在表面树脂组合物和基质树脂组合物中,组分(A)(即,具有低于230℃的熔点的一种或多种组(I)全脂族聚酰胺)和/或组分(B)(即,选自具有至少250℃的熔点的组(II)聚酰胺的一种或多种全脂族聚酰胺)不同并且/或者所述组分(A)和/或(B)的量不同。
优选地,基质树脂组合物包含(A)一种或多种组(I)聚酰胺和(B)选自组(II)聚酰胺的一种或多种聚酰胺的共混物,重量比(A∶B)为约1∶99至约95∶5,更优选为约15∶85至约85∶15。还更优选地,基质树脂组合物包含(A)一种或多种组(I)聚酰胺和(B)选自组(II)聚酰胺的一种或多种聚酰胺的共混物(重量比(A∶B)为约20∶80至约30∶70)或单独地选自一种或多种聚酰胺B。
优选地,表面树脂组合物包含(A)一种或多种组(I)聚酰胺和(B)选自组(II)聚酰胺(B)的一种或多种聚酰胺的共混物,重量比(A∶B)为约1∶99至约95∶5,更优选为约15∶85至约85∶15,并且还更优选为约40∶60至约60∶40。
聚酰胺为一种或多种二羧酸和一种或多种二胺、和/或一种或多种氨基羧酸的缩合产物,和/或一种或多种环状内酰胺的开环聚合反应产物。
所述一种或多种全脂族聚酰胺(A)和(B)由脂族和脂环族单体(例如二胺、二羧酸、内酰胺、氨基羧酸、以及它们的反应性等同物)形成。合适的氨基羧酸为11-氨基十二烷酸。合适的内酰胺包括己内酰胺和十二内酰胺。在本发明的上下文中,术语“全脂族聚酰胺”也是指衍生自两种或更多种此类单体的共聚物以及两种或更多种全脂族聚酰胺的共混物。可使用直链、支化和环状的单体。
全脂族聚酰胺中所包含的羧酸单体为脂族羧酸,例如己二酸(C6)、庚二酸(C7)、辛二酸(C8)、壬二酸(C9)、癸二酸(C10)、十二烷二酸(C12)和十四烷二酸(C14)。优选地,所述一种或多种全脂族聚酰胺(A)和(B)的脂族二羧酸选自己二酸和十二烷二酸。本文所述的一种或多种全脂族聚酰胺(A)和(B)包含如此前所述的脂族二胺。优选地,根据本发明的一种或多种全脂族聚酰胺共聚物(A)和(B)的一种或多种二胺单体选自丁二胺和己二胺。全脂族聚酰胺的合适的例子包括聚酰胺6;聚酰胺6,6;聚酰胺4,6;聚酰胺6,10;聚酰胺6,12;聚酰胺6,14;聚酰胺6,13;聚酰胺6,15;聚酰胺6,16;聚酰胺11;聚酰胺12;聚酰胺9,10;聚酰胺9,12;聚酰胺9,13;聚酰胺9,14;聚酰胺9,15;聚酰胺6,16;聚酰胺9,36;聚酰胺10,10;聚酰胺10,12;聚酰胺10,13;聚酰胺10,14;聚酰胺12,10;聚酰胺12,12;聚酰胺12,13;聚酰胺12,14。用于本发明的聚酰胺组合物的全脂族聚酰胺(B)的优选例子为聚(己二酰己二胺)(聚酰胺66、PA66、也称为尼龙66)和聚(己二酰丁二胺)(聚酰胺46、PA46、也称为尼龙46)。
优选的具有低于230℃的熔点的组(I)聚酰胺包含选自以下的全脂族聚酰胺:聚(ε-己内酰胺)(PA6)和聚(癸二酰戊二胺)(PA510)、聚(十二烷二酰戊二胺)(PA512)、聚(ε-己内酰胺/己二酰己二胺)(PA6/66)、聚(ε-己内酰胺/癸二酰己二胺)(PA6/610)、聚(ε-己内酰胺/十二烷二酰己二胺)(PA6/612)、聚(十三烷二酰己二胺)(PA613)、聚(十五烷二酰己二胺)(PA615)、聚(ε-己内酰胺/己二酰己二胺/癸二酰己二胺)(PA6/66/610)、聚(ε-己内酰胺/己二酰己二胺/十二烷二酰己二胺)(PA6/66/612)、聚(ε-己内酰胺/己二酰己二胺/癸二酰己二胺/十二烷二酰己二胺)(PA6/66/610/612)、聚(己二酰2-甲基戊二胺/己二酰己二胺/)(PA D6/66)、聚(癸二酰癸二胺)(PA1010)、聚(十二烷二酰癸二胺)(PA1012)、聚(11-氨基十一烷酰胺)(PA11)、聚(12-氨基十二烷酰胺)(PA12)、PA6,12、PA12,12。
优选的具有至少250℃的熔点的组(II)聚酰胺是选自以下的聚酰胺:聚(己二酰己二胺)(PA66)、聚(ε-己内酰胺/己二酰己二胺)(PA6/66)、(PA6/66/610)、聚(ε-己内酰胺/己二酰己二胺/十二烷二酰己二胺)(PA6/66/612)、聚(ε-己内酰胺/己二酰己二胺/癸二酰己二胺/十二烷二酰己二胺)(PA6/66/610/612)、聚(己二酰2-甲基戊二胺/己二酰己二胺/)(PAD6/66)、聚(己二酰丁二胺)(PA46)。
本发明的一个实施例包含基质树脂组合物和表面树脂组合物,其包含PA6(组(I)聚酰胺A)和PA66(组(II)聚酰胺B),A∶B比率为25∶75。
本发明的一个优选的实施例包含基质树脂组合物(其包含PA6(组(I)聚酰胺A)和PA66(组(II)聚酰胺B),A∶B比率为25∶75)和表面树脂组合物(其包含PA6(组(I)聚酰胺A)和PA66(组(II)聚酰胺B),A∶B比率为50∶50)。
本发明的另一个优选的实施例包含基质树脂组合物(其包含PA66(组(II)聚酰胺B))和表面树脂组合物(其包含PA6(组(I)聚酰胺A)和PA66(组(II)聚酰胺B),A∶B比率为50∶50)。
本文所述的表面树脂组合物和/或基质树脂组合物还可包含一种或多种抗冲改性剂、一种或多种热稳定剂、一种或多种氧化稳定剂、一种或多种紫外线稳定剂、一种或多种阻燃剂或它们的混合物。
本文所述的表面树脂组合物和/或基质树脂组合物还可包含一种或多种增强剂,例如玻璃纤维、玻璃片、碳纤维、碳纳米管、云母、硅灰石、碳酸钙、滑石、煅烧的粘土、高岭土、硫酸镁、硅酸镁、氮化硼、硫酸钡、二氧化钛、碳酸钠铝、钡铁氧体和钛酸钾。可根据具体情况,当存在一种或多种增强剂时,其含量为1重量%或约1重量%至60重量%或约60重量%,优选为1重量%或约1重量%至40重量%或约40重量%,或更优选为1重量%或约1重量%至35重量%或约35重量%,所述重量百分比是基于所述表面树脂组合物或所述基质树脂组合物的总重量计的。
如上所述,基质树脂组合物和表面树脂组合物可相同或不同。为了提高纤维材料的浸渍速率,可降低组合物的熔融粘度,尤其是基质树脂组合物的熔融粘度。
本文所述的表面树脂组合物和/或基质树脂组合物还可包含改性剂和其它成分,无限制地包括流动促进添加剂、润滑剂、抗静电剂、着色剂(包括染料、颜料、炭黑等)、成核剂、结晶促进剂、以及聚合物配混领域已知的其它加工助剂。
上述填料、改性剂和其它成分可以本领域熟知的量和形式存在于组合物中,包括所谓的纳米材料的形式,其中颗粒的至少一种尺寸在1至1000nm的范围内。
优选地,表面树脂组合物和基质树脂组合物为熔融混合的共混物,其中所有的聚合物组分都均匀分散在彼此中,并且所有的非聚合物成分都均匀分散在聚合物基质中并通过聚合物基质粘结,使得共混物形成一个统一整体。可使用任何熔融混合方法来混合本发明的聚合物组分和非聚合物成分。例如,可将聚合物组分和非聚合物成分加入熔融搅拌器中,例如单螺杆或双螺杆挤出机;搅拌机;单螺杆或双螺杆捏合机;或班伯里密炼机。可通过单步加料一次性完成,以分步方式加入,然后进行熔融混合。当以分步方式加入聚合物组分和非聚合物成分时,首先加入部分聚合物组分和/或非聚合物成分并进行熔融混合,随后再加入剩余的聚合物组分和非聚合物成分,进一步进行熔融混合,直至获得充分混合的组合物。
根据最终应用,根据本发明的复合结构可具有任何形状。在一个优选的实施例中,根据本发明的复合结构为片材结构的形式。复合结构可为柔性的,在此情况下可将其卷起。
所述复合结构可由如下方法制成,所述方法包括用基质树脂组合物浸渍纤维材料的步骤,其中所述复合结构表面的至少一部分由表面树脂组合物制成。优选地,通过热压经基质树脂浸渍纤维材料。在热压期间,纤维材料、基质树脂组合物和表面树脂组合物经受热和压力,从而使树脂组合物熔融并渗透穿过纤维材料,从而浸渍所述纤维材料。
通常,热压在以下条件下进行:压力介于2和100巴之间,并且更优选介于10和40巴之间,和温度高于基质树脂组合物和表面树脂组合物的熔点,优选高于该熔点至少约20℃,从而能够适当的浸渍。加热可通过多种方式来完成,包括接触加热、辐射气体加热、红外线加热、对流或强制对流空气加热、感应加热、微波加热或它们的组合。
可通过静态方法或通过连续方法(也称为动态方法)来施加浸渍压,出于速度原因,连续方法是优选的。浸渍方法的例子无限制地包括真空模塑、模内涂覆、横向模挤出、拉挤、线材涂覆型方法、层压、压印、隔膜成型或加压模塑,层压是优选的。在层压期间,通过加热区中相对的受压辊或带,将热和压力施加到纤维材料、基质树脂组合物和表面树脂组合物,然后优选通过加压装置在冷却区连续施加压力,以完成固结并将经浸渍的纤维材料冷却。层压技术的例子包括但不限于压延、平台层压和双带压力机层压。当将层压用作浸渍方法时,优选使用双带压力机进行层压。
如果基质树脂组合物和表面树脂组合物不同,则当将重叠注塑性树脂组合物施用到复合结构上时,表面树脂组合物总是面对第一组件的环境以便可被触及。
可采用常规方法将基质树脂组合物和表面树脂组合物施用到纤维材料,这些方法为例如粉末涂覆、膜层压、挤出涂覆或其中两种或更多种方法的组合,前提条件是将表面树脂组合物施用在复合结构表面的至少一部分上,所述表面暴露于第一组件的环境。
在粉末涂覆方法期间,将通过常规碾磨方法获得的聚合物粉末施用到纤维材料。可通过散射、喷洒、喷涂、热喷涂或火焰喷涂、或流化床涂覆方法将粉末施用到纤维材料上。任选地,粉末涂覆方法还可包括对纤维材料上的粉末进行后烧结的步骤。将基质树脂组合物和表面树脂组合物施用到纤维材料,使得第一组件表面的至少一部分由表面树脂组合物制成。随后,对粉末涂覆的纤维材料进行热压,并可任选地对加压区之外的粉末涂覆的纤维材料进行预热。
在膜层压期间,将一个或多个由基质树脂组合物制成的膜和一个或多个由表面树脂组合物制成的膜例如通过层叠施用到纤维材料,这些膜事先通过本领域已知的常规挤出方法获得,例如吹塑膜挤出、流延膜挤出和流延片材挤出。随后,对组件进行热压操作,所述组件包含一个或多个由基质树脂组合物制成的膜和一个或多个由表面树脂组合物制成的膜以及一种或多种纤维材料。在所得的第一组件中,膜熔融并渗透包围所述纤维材料,成为所述纤维材料周围的聚合物连续统一体。
在挤出涂覆期间,将由基质树脂组合物制成的粒料和/或颗粒以及由表面树脂组合物制成的粒料和/或颗粒熔融并挤出穿过一个或多个平模,以形成一个或多个熔帘,随后通过铺放所述一个或多个熔帘而将熔帘施用到纤维材料上。随后,对包含基质树脂组合物、表面树脂组合物和一种或多种纤维材料的组件进行热压。
根据最终应用,通过步骤i)获得的复合结构可成型为期望的几何形状或构型,或以片材形式使用。制备根据本发明的复合结构的方法还可包括将复合结构成型的步骤ii),所述步骤在浸渍步骤i)之后发生。将通过步骤i)获得的复合结构成型的步骤可通过压塑、压印、或者利用热和/或压力的任何技术来完成。优选地,使用液压式压型机来施加压力。在压塑或压印期间,将复合结构预热到高于表面树脂组合物的熔融温度的温度,然后转移到形成或成型装置例如压型机中,其包括具有腔体的模具,所述腔体具有最终期望的几何形状的形状,借此将第一组件成型为期望的构型,然后在冷却到低于表面聚酰胺树脂组合物的熔融温度并优选低于基质树脂组合物的熔融温度的温度后,从压机或模具中取出。
本发明的复合结构尤其适于用聚酰胺重叠注塑性树脂组合物进行重叠注塑。可对所述重叠注塑性树脂组合物使用任何聚酰胺树脂。当重叠注塑性树脂组合物选自包含选自(B)的聚酰胺组合物或独立地选自包含以下物质的共混物的聚酰胺组合物时获得了特别良好的粘附性:(A)选自具有低于230℃的熔点的组(I)聚酰胺的一种或多种全脂族聚酰胺,和(B)选自具有至少250℃的熔点的组(II)聚酰胺的一种或多种全脂族聚酰胺。
根据本发明的复合结构可用于许多应用,例如用作机动车组件、卡车组件、商用飞机组件、航空航天器组件、轨道组件、家用电器组件、计算机硬件组件、手持式装置组件、娱乐和体育设施组件、机器结构组件、建筑结构组件、光伏设备结构组件或机械装置结构组件。
机动车应用的例子包括但不限于座椅组件和座椅框架、引擎盖支架(enginecover brackets)、引擎架、悬吊臂和架、备胎槽、底盘加强件、车身底板、前端模块、转向柱框架(steering columns frame)、仪表板、车门系统、车身面板(例如水平车身面板和门面板)、后挡板、硬顶轿车框架结构、敞篷车顶框架结构、顶板结构、引擎盖、传动装置和传能组件的外壳、油底壳、气囊外壳罐、机动车内部撞击结构、引擎支架、交叉车横梁、缓冲梁、行人安全横梁、隔火墙、后置物板、交叉车舱壁、压力容器(例如制冷剂瓶和灭火器以及卡车压缩空气制动系统容器)、混合内燃机/电动车电池托架、机动车悬吊横臂和控制臂、悬吊平衡杆接杆、叶片弹簧、车轮、休旅车和摩托车摆臂、挡泥板、车顶框架以及油箱盖板。
家用电器的例子无限制地包括洗衣机、烘干机、冰箱、空调和暖气。娱乐和体育设施的例子无限制地包括单线滚轴溜冰鞋组件、棒球棒、曲棍球棍、雪橇和滑雪板固定器、背包背衬和框架以及自行车架。机器结构组件的例子包括电气/电子部件,例如手持式电子装置外壳、计算机外壳。
实例
以下材料用于制备根据本发明和比较例的复合结构。
材料
在实例和比较例中使用的组合物中包含以下材料。
来自组II的聚酰胺(B)(表1和2中的PA1):由己二酸和1,6-己二胺制成的组II聚酰胺,其具有大约32000道尔顿的重均分子量。PA1具有约260℃至约265℃的熔点和约40℃至约70℃的玻璃化转变温度。PA1被称为PA6,6并且可例如从E.I.du Pont de Nemours andCompany商购获得。
来自组I的聚酰胺(A)(表1和2中的PA2):由ε-己内酰胺制成的组I聚酰胺,其具有约220℃的熔点。PA2被称为PA6并且可例如从BASFcorporation商购获得。
制备膜
用于本实例(在表1和2中缩写为“E”)和比较例(在表1和2中缩写为“C”)的树脂组合物通过在双螺杆挤出机中在约280℃下对所述成分进行熔融或熔融共混来制备。在约280℃下离开该挤出机经过适配器和膜模具时,所述组合物浇注到约100℃的浇注辊上,对于C1、E1和E2的基质树脂组合物(表1)和C1的表面树脂组合物(表1)形成约102微米厚的膜,对于实例E1和E2的表面树脂组合物(表1)形成约200微米厚的膜,对于E3和C2的基质和表面树脂组合物(表2)均形成约250微米厚的膜。所述膜的厚度通过拉动的速率进行控制。
制备表1的复合结构E1、E2和C1
所述复合结构C1(比较)、E1和E2首先通过制备层压体来制备,所述层压体通过对八个具有约102微米厚度并由PA1制成的层以及三个织造连续玻璃纤维纺织品(由E-玻璃纤维制备,所述E-玻璃纤维具有17微米的直径,0.4%的基于硅烷的上浆,以及1200g/km的标称粗纱特克斯,其已被织造成具有600g/m2面积重量的2/2斜纹织物(平衡编织物))层以如下顺序进行堆叠来制备:两个由PA1制成的层、一个织造连续玻璃纤维纺织品层、两个由PA1制成的层、一个织造连续玻璃纤维纺织品层、两个由PA1制成的层、一个织造连续玻璃纤维纺织品层和两个由PA1制成的层。
用配有反转钢带的等压双压床制备所述层压体,它们都由Held GmbH提供。不同的膜以此前所规定的堆叠顺序从开卷机中进入该机器。加热区为约2000mm长,并且冷却区为约1000mm长。在不释放压力的情况下保持加热和冷却。在以下条件下制备所述层压体:1m/min的层压速率、360℃的最大机器温度和40巴的层压压力。如此获得的层压体具有约1.5mm的总体厚度。
将约200微米并由表1中描述的E1和E2的表面聚酰胺树脂组合物制成的膜应用于上述层压体,从而形成所述复合结构。用具有适配器和膜模具以及油加热的浇注辊的28mmW&P挤出机制备包含表面聚酰胺树脂组合物的膜。将所述挤出机、适配器和模具温度设为280℃,并且将所述浇注辊的温度设为100℃。通过具有8英寸平板的44-225型Dake压机(Grand Haven,Mich)(压力范围0-25K)压塑所述膜来形成复合结构。将6×6″的层压体样本置于模具中,并在约300℃的温度下用约3KPsi的压力将膜压到层压体表面上约2分钟,然后用大约6Kpsi的压力再压约3分钟,并且随后冷却至室温。包含由表1中所述的E1或E2的表面聚酰胺树脂组合物制成的表面、基质树脂组合物PA1和纤维材料的复合结构具有约1.5mm的总体厚度。
制备表2的复合结构E3和C2
通过对表2中所示的多层组合物膜和织造连续玻璃纤维纺织品(由E-玻璃纤维制备,所述E-玻璃纤维具有17微米的直径,用0.4%的基于硅烷的上浆剂上浆,以及1200g/km的标称粗纱特克斯,其已被织造成具有600g/m2面积重量的2/2斜纹织物(平衡编织物))以如下顺序进行层压来制备表2的复合结构E3和C2:两层表面树脂组合物膜、一层织造连续玻璃纤维纺织品、两层基质树脂组合物膜、一层织造连续玻璃纤维纺织品、两层基质树脂组合物膜、一层织造连续玻璃纤维纺织品、和两层表面树脂组合物膜。
通过具有8英寸平板的44-225型Dake压机(Grand Haven,Mich)(压力范围0-25K)压塑表2的复合结构。将如上所述的膜和玻璃纺织品层的6×6″样本置于模具中并加热至约320℃的温度,在该温度下无压力保持2分钟,然后在320℃的温度下在以下压力下加压:约6巴下约2分钟,然后约22巴再约2分钟,并且然后约45巴下再约2分钟;随后将其冷却至环境温度。由此形成的复合结构具有约1.6mm的厚度。
表1的复合结构C1、E1和E2的粘结强度
当用包含PA1和30重量%玻璃纤维(所述重叠注塑性树脂的总体组合物的百分比)的重叠注塑性树脂组合物重叠注塑复合结构C1、E1和E2时,所述粘结强度分别为0、86和121MPa,这展示出当与来自单一组聚酰胺的聚酰胺相比时,选自组1的聚酰胺与选自组II的聚酰胺的共混物对于重叠注塑性树脂形成强粘结强度的更优的能力。
通过将1.7mm的重叠注塑性树脂组合物重叠注塑到如上所述获得的复合结构上来完成所述重叠注塑。将包含由表1中所列的表面树脂组合物制成的表面、表1中所列的基质树脂组合物和上述纤维材料的复合结构C1、E1和E2切割成5×5″(约127mm×127mm)的样本并且置于180℃下的加热室中3分钟。然后用机械手臂将所述复合结构迅速转移到恩格尔(Engel)立式压力机的模具腔体中并通过恩格尔模塑机用包含PA1和30重量%玻璃纤维(所述重叠注塑性树脂的总体组合物的百分比)的重叠注塑性树脂组合物进行重叠注塑。从离开加热室到与该重叠注塑性树脂接触的转移时间为9秒。在120℃下油加热所述模具。将所述注射机设为280℃。
将包含根据如上所述制备的E1、E2和C1的重叠注塑的复合结构的5×5″样本切割成3/4″×5″的测试样本(约19mm×约127mm),并且通过切割所述重叠注塑的部件直至该重叠注塑的部件与所述复合结构的界面有凹口。通过在大约所述测试样本中间处(纵向)的宽度而制备所述凹口。经由3点弯曲法(改进的ISO-178)在凹口测试样本上测量所述重叠注塑的树脂组合物与所述复合结构之间的粘结强度。设备和几何形状是根据ISO方法178,弯曲样本,该样本具有负荷边缘处于跨度中心的2.0″(约51mm)的支撑件宽度。样本的重叠注塑的部件以拉伸侧(外跨度)倚靠在两个侧支撑件上(相距2″(约51mm)),而具有单一支撑件(负荷)的压痕在复合结构样本上的压缩侧(内跨度)。在该测试几何形状中,所述样本中的凹口向下(拉伸侧)。凹口被偏离中心1/4″(远离负荷1/4″)放置。以2mm/min进行所述测试。运行所述测试直至看见所述样本的两个部件之间分离或断裂(分层)。记录该点处的应力。
表2中的复合结构E3和C2的弯曲强度
使用具有金刚石刀刃的MK-377瓷砖锯(Tile Saw)并以水作为润滑剂将表2中的复合结构E3和C2切割成1/2″(约12.7mm)×2.5″(约64mm)的长形测试样本(条块)。经由3点弯曲测试对所述测试样本进行弯曲强度测试。设备和几何形状是根据ISO方法178,弯曲样本,所述样本具有负荷边缘处于跨度中心的2.0″的支撑件宽度。用1KN的负荷以2mm/min进行所述测试直至断裂。结果示于表2中,对于复合结构E3和C2分别为380和332MPa,这展示出当与来自单一组聚酰胺的聚酰胺制成的复合结构相比时,由选自组1的聚酰胺与选自组II的聚酰胺的共混物制成的复合结构的优异的弯曲强度。
表1
表2
Claims (14)
1.复合结构,所述复合结构具有表面并且包含纤维材料,所述表面的至少一部分由表面树脂组合物制成,所述纤维材料选自非织造结构、纺织品、纤维絮片以及它们的组合,所述纤维材料经基质树脂组合物浸渍,其中所述表面树脂组合物选自包含以下物质的共混物的聚酰胺组合物:(A)选自具有低于230℃的熔点的组(I)聚酰胺的一种或多种全脂族聚酰胺,和(B)选自具有至少250℃的熔点的组(II)聚酰胺的一种或多种全脂族聚酰胺,并且其中所述基质树脂组合物独立地选自(B)或独立地选自(A)与(B)的共混物,
其中所述表面树脂组合物的所述选自组(I)聚酰胺的一种或多种聚酰胺(A)与所述选自组(II)聚酰胺的一种或多种聚酰胺(B)的重量比(A∶B)为15∶85至85∶15。
2.根据权利要求1所述的复合结构,其中所述纤维材料由玻璃纤维、碳纤维、芳族聚酰胺纤维、天然纤维或它们的混合物制成。
3.根据权利要求2所述的复合结构,其中所述纤维材料由玻璃纤维制成。
4.根据权利要求1所述的复合结构,其中所述纤维材料为所述复合结构的30体积%至60体积%。
5.根据权利要求1所述的复合结构,还包含一种或多种添加剂,所述添加剂选自热稳定剂、氧化稳定剂、增强剂和阻燃剂或它们的组合。
6.根据前述权利要求中任一项所述的复合结构,其中所述选自组(I)聚酰胺的一种或多种全脂族聚酰胺选自PA6、PA510、PA512、PA6/66、PA6/610、PA6/612、PA613、PA615、PA6/66/610、PA6/66/612、PA6/66/610/612、PA D6/66、PA1010、PA1012、PA11、PA12、PA612、PA1212。
7.根据权利要求1-5中任一项所述的复合结构,其中所述选自组(II)聚酰胺的一种或多种全脂族聚酰胺选自PA66、PA6/66、PA6/66/610、PA6/66/612、PA6/66/610/612、PA D6/66、PA46。
8.根据权利要求1所述的复合结构,其中所述基质树脂组合物的所述选自组(I)聚酰胺的一种或多种聚酰胺(A)与所述选自组(II)聚酰胺的一种或多种聚酰胺(B)的重量比(A∶B)介于1∶99至95∶5之间。
9.根据权利要求1所述的复合结构,其中所述基质树脂组合物的所述选自组(I)聚酰胺的一种或多种聚酰胺(A)与所述选自组(II)聚酰胺的一种或多种聚酰胺(B)的重量比(A∶B)为20∶80至30∶70。
10.根据权利要求1所述的复合结构,其中所述表面树脂组合物的所述选自组(I)聚酰胺的一种或多种聚酰胺(A)与所述选自组(II)聚酰胺的一种或多种聚酰胺(B)的重量比(A∶B)为20∶80至60∶40。
11.根据权利要求1所述的复合结构,其中组(I)聚酰胺(A)单独地或以组合方式包含PA6、PA6/12、A10/10。
12.根据权利要求1所述的复合结构,其中组(II)聚酰胺(B)单独地或以组合方式包含PA66、PA46。
13.根据权利要求1所述的复合结构,所述复合结构为机动车组件、卡车组件、商用飞机组件、航空航天器组件、轨道组件、家用电器组件、计算机硬件组件、手持式装置组件、娱乐和体育设施组件、机器结构组件、建筑结构组件、光伏设备结构组件或机械装置结构组件的形式。
14.制备根据权利要求1所述的具有表面的复合结构的方法,所述方法包括以下步骤:
i)用基质树脂组合物浸渍纤维材料,所述纤维材料选自非织造结构、纺织品、纤维絮片以及它们的组合,所述纤维材料经基质树脂组合物浸渍,
其中所述复合结构表面的至少一部分由表面树脂组合物制成,并且
其中所述表面树脂组合物选自包含以下物质的共混物的聚酰胺组合物:(A)选自具有低于230℃的熔点的组(I)全脂族聚酰胺的一种或多种全脂族聚酰胺;和(B)选自具有至少250℃的熔点的组(II)聚酰胺的一种或多种全脂族聚酰胺,并且其中所述基质树脂组合物独立地选自(B)或独立地选自(A)与(B)的共混物,
其中所述表面树脂组合物的所述选自组(I)聚酰胺的一种或多种聚酰胺(A)与所述选自组(II)聚酰胺的一种或多种聚酰胺(B)的重量比(A∶B)为15∶85至85∶15。
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