CN107406610B - 含发泡剂的泡沫材料的纤维增强 - Google Patents

含发泡剂的泡沫材料的纤维增强 Download PDF

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Publication number
CN107406610B
CN107406610B CN201580076648.XA CN201580076648A CN107406610B CN 107406610 B CN107406610 B CN 107406610B CN 201580076648 A CN201580076648 A CN 201580076648A CN 107406610 B CN107406610 B CN 107406610B
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foam
blowing agent
fibers
fiber
molded article
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CN107406610A (zh
Inventor
H·鲁克德舍尔
R·阿伯特
R·斯泰恩
D·朗格-谢德尔
T·迪尔曼
B·D·S·萨姆帕斯
P·古特曼
A·泰尔努瓦尔
M·哈滕斯泰恩
A·科尔基斯
A·莫里诺
G·道恩
M·C·马丁
P·默克尔
T·基西亚克
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BASF SE
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BASF SE
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Abstract

本发明涉及一种制造包含至少一个纤维(F)的由含发泡剂的泡沫制成的模制品的方法,所述至少一个纤维(F)被部分地引入含发泡剂的泡沫材料中。相应纤维(F)的未被泡沫材料包围的两端因而从相应模制品的一侧突出。本发明还涉及模制品本身。本发明还涉及一种板材,其包括至少一个根据本发明的方法制造的模制品和至少一个另外的层(S1)。本发明还涉及本发明的板材的制造及其用途,例如作为风力涡轮机中的转子叶片。

Description

含发泡剂的泡沫材料的纤维增强
本发明涉及一种制造包含至少一个纤维(F)的由含发泡剂的泡沫制成的模制品的方法,其中至少一个纤维(F)被部分地引入含发泡剂的泡沫中。各纤维(F)的未被含发泡剂的泡沫包围的两端因而从相应模制品的一侧突出。本发明还提供了模制品本身。本发明进一步提供了一种板材,其包括至少一个通过本发明的方法制造的模制品和至少一个另外的层(S1)。本发明还提供了本发明的板材的制造及其用途,例如作为风力涡轮机中的转子叶片。
WO 2006/125561涉及一种用于制备增强多孔材料的方法,其中在第一工艺步骤中,在多孔材料中产生从多孔材料的第一表面延伸至第二表面的至少一个孔。在多孔材料的第二表面的另一侧上,提供至少一个纤维束,用针牵引所述纤维束穿过孔至多孔材料的第一侧。然而,在针抓持住纤维束之前,首先拉动针穿过来自多孔材料的第一侧的特定孔。此外,根据WO 2006/125561方法的结果,纤维束部分地处于多孔材料内,因为其填充了相应的孔,并且相应的纤维束在各侧部分地从多孔材料的第一表面和第二表面突出。
通过WO 2006/125561中记载的方法,可以制备包括所述多孔材料的芯和至少一个纤维束的夹层状部件。可将树脂层和纤维增强树脂层施加到该芯的表面上,以便制造实际的夹层状部件。用于形成夹层状部件的芯的多孔材料可以例如是聚氯乙烯或聚氨酯。有用的纤维束的实例包括碳纤维、尼龙纤维、玻璃纤维或聚酯纤维。
然而,WO 2006/125561没有公开其用于制造夹层状部件中的芯的多孔材料包括含发泡剂的泡沫。根据WO 2006/125561的夹层状部件适用于飞机构造。
WO 2011/012587涉及制备用于由复合材料制成的板材的具有一体化架桥纤维的芯的另外的方法。通过借助于针拉动提供在由轻质材料制成的称为“坯”的物体的表面上的架桥纤维部分或完全地穿过所述坯而制备芯。该“坯”可由聚氨酯泡沫、聚酯泡沫、聚对苯二甲酸乙二醇酯泡沫、聚氯乙烯泡沫或酚醛泡沫特别是聚氨酯泡沫形成。所使用的纤维原则上可以是任何种类的单根或多根线和其它纱线。
这样制备的芯又可为由复合材料制成的板材的一部分,其中所述芯被树脂基质以及树脂基质与夹层状构造中的纤维的组合在一侧或两侧包围。然而,WO 2011/012587没有公开含发泡剂的泡沫可用于制备相应的芯材料。
WO 2012/138445涉及使用多个具有低密度的多孔材料的纵向条来制造复合芯板的方法。在单个条之间引入双层纤维垫,这借助于树脂的使用使得单个条粘合而形成复合芯板。根据WO 2012/138445,形成纵向条的具有低密度的多孔材料选自轻木、弹性泡沫和纤维增强复合泡沫。在单个条之间以双层形式引入的纤维垫可例如为多孔玻璃纤维垫。用作粘合剂的树脂可例如为聚酯、环氧树脂或酚醛树脂,或热活化热塑性塑料例如聚丙烯或PET。然而,WO 2012/138445没有公开可以将单个的纤维或纤维束掺入多孔材料中用于增强。根据WO 2012/138445,仅将在通过树脂粘合单个条的情况下另外构成粘合元件而得到芯材料的纤维垫用于该目的。
GB-A 2 455 044公开了一种制备多层复合制品的方法,其中在第一工艺步骤中,提供多个热塑性材料珠粒和发泡剂。热塑性材料为包含至少20重量%至70重量%的聚苯醚(PPO)的聚苯乙烯(PS)和PPO的混合物。在第二工艺步骤中,使珠粒发泡,并且在第三工艺步骤中,将其焊接在模具中以形成热塑性材料的闭孔泡沫而得到模制品,闭孔泡沫呈现模具的形状。在下一工艺步骤中,将纤维增强材料层施加到闭孔泡沫的表面上,使用环氧树脂进行各个表面的附着。然而,GB-A 2 455 044没有公开可以将纤维材料引入至多层复合制品的芯中。
在WO 2009/047483中还公开了(与GB-A 2 455 044中的那些)类似的方法和类似的多层复合制品。这些多层复合制品例如适合用于转子叶片(风力涡轮机中)或用作船体。
US-B 7,201,625公开了一种制造泡沫产品的方法和泡沫产品本身,其可用于例如运动行业中作为冲浪板。泡沫产品的芯通过模制泡沫形成,例如基于聚苯乙烯泡沫。该模制泡沫在特定模具中制造,外部塑料皮包围该模制泡沫。外部塑料皮可以例如为聚乙烯膜。然而,US-B 7,201,625也没有公开用于材料增强的纤维可存在于模制泡沫中。
US-B 6,767,623公开了具有基于粒径在2~8mm范围内且堆积密度在10~100g/L范围内的颗粒的模制聚丙烯泡沫芯层的夹层板。此外,所述夹层板包括两个纤维增强聚丙烯的外层,其中各个外层围绕芯布置而形成夹层。出于装饰目的,另外的层可任选存在于夹层板中。外层可包含玻璃纤维或其它聚合物纤维。
EP-A 2 420 531公开了基于诸如聚苯乙烯的聚合物的挤出泡沫,其中存在至少一种粒径≤10μm的矿物填料和至少一种成核剂。这些挤出泡沫因其改善的刚度而引人注目。另外记载了用于制造基于聚苯乙烯的这种挤出泡沫的相应挤出方法。挤出泡沫可具有闭孔。然而,EP-A 2 480 531并未表明挤出泡沫包含纤维。
WO 2005/056653涉及由包含填料的可发性聚合物珠粒形成的模制泡沫。所述模制泡沫可通过焊接由包含填料的可发性热塑性聚合物珠粒形成的预发泡泡沫珠粒而获得,模制泡沫的密度在8~300g/L的范围内。热塑性聚合物珠粒尤其包括苯乙烯聚合物。所使用的填料可以是粉状无机物质、金属、白垩、氢氧化铝、碳酸钙或氧化铝;或者珠粒或纤维形式的无机物质,例如玻璃珠、玻璃纤维或碳纤维。
US 3,030,256涉及通过使用纤维增强由泡沫或借助于发泡剂发泡的聚合物制备的芯而制造的层压板。所记载的用于芯的材料为发泡和挤出的聚苯乙烯以及酚、环氧化物和聚氨酯。为了引入纤维,使用针从芯的第一侧至芯的第二侧产生孔,并使用相同的针将纤维束通过孔从第二侧拉到第一侧,使得纤维束部分地在芯内且部分地从第一侧和第二侧突出。将纤维材料以相对于芯的厚度方向为0°的角度引入至芯中。
本发明的目的在于提供一种用于制造纤维增强模制品的新方法和提供新的纤维增强板材。
根据本发明,通过用于制造包含至少一个纤维(F)的模制品的方法来实现该目的,其中将至少一个纤维(F)部分地引入至由含发泡剂的泡沫制成的模制品内于所述含发泡剂的泡沫中,其结果是,纤维(F)在模制品内以纤维区域(FB2)存在并被含发泡剂的泡沫包围,而纤维(F)的纤维区域(FB1)从模制品的第一侧突出并且纤维(F)的纤维区域(FB3)从模制品的第二侧突出,其中所述模制品包含每m2超过1000个纤维(F)。
本发明还提供了一种用于制造包含至少一个纤维(F)的模制品的方法,其中将至少一个纤维(F)部分地引入至由含发泡剂的泡沫制成的模制品内于所述含发泡剂的泡沫中,其结果是,纤维(F)在模制品内以纤维区域(FB2)存在并被含发泡剂的泡沫包围,而纤维(F)的纤维区域(FB1)从模制品的第一侧突出并且纤维(F)的纤维区域(FB3)从模制品的第二侧突出。
以下的细节和优选适用于所述制造模制品的方法的两个实施方案。
本发明的方法提供具有改进的机械性能的模制品。此外,本发明的方法减少了含发泡剂的泡沫的稳定化时间。所述情况特别是由于将纤维(F)引入至含发泡剂的泡沫中而实现了更快速的发泡剂交换,特别是更快速的气体交换,连同与环境更快速的热交换。特别是在使用发泡剂逐渐脱附的泡沫/发泡剂组合的情况下,这明显地减少了在制造含发泡剂的泡沫之后含发泡剂的泡沫通常所需的储存时间。因此,可获得对发泡剂和发泡剂含量的更多选择而同时具有短的稳定化时间,从而可以彼此独立地优化泡沫的制造过程、所得泡沫的结构和熟化时间(发泡剂脱附所需的时间)。
当制造含发泡剂的泡沫之后尽可能快地进行本发明的方法时,也可实现有利的效果。在这种情况下,含发泡剂的泡沫具有特别低的缝合阻力。因此,减少了所需的缝纫力,这明显地降低了在本发明方法的优选实施方案中使用的针的磨损。另外,可以提高制造能力。由于热交换和发泡剂交换(发泡剂脱附),含发泡剂的泡沫额外地收缩,其结果为纤维(F)在含发泡剂的泡沫中更好地固定。因此,根据本发明制造的模制品中纤维(F)的拉脱阻力显著上升。
根据本发明制造的模制品还有利地具有低树脂吸收和同时良好的界面结合的特征。当根据本发明制造的模制品被进一步加工以得到本发明的板材时,这种效果是重要的。
根据本发明,通过对根据本发明制造的模制品或由其产生的板材中的含发泡剂的泡沫的纤维增强,能够进一步改善粘合同时降低树脂吸附。根据本发明,纤维(单独地或优选以纤维束形式)可有利地首先以干燥形式和/或通过机械方法被引入至含发泡剂的泡沫中。纤维或纤维束与各个含发泡剂的泡沫表面并非平齐地而是超出地放置,因此能够改进与本发明的板材中相应外层的粘合或直接连接。根据本发明,当施加到本发明的模制品上的外层为形成板材的至少一个另外的层(S1)时尤其如此。优选施加可相同或不同的两个层(S1)。更优选地,将两个相同的层(S1),特别是两个相同的纤维增强树脂层施加到根据本发明制造的模制品的相对侧上,以形成本发明的板材。这种板材也称为“夹层材料”,在这种情况下,根据本发明制造的模制品也可称为“芯材料”。
因此,本发明的板材由于低的树脂吸附和良好的剥离强度而引人注目。此外,通过选择纤维类型及其比例和布置,可以受控的方式建立高的强度和刚度特性。低树脂吸附的效果是重要的,因为在使用这种板材(夹层材料)的情况下,共同的目标是应以最小的重量提高结构特性。在使用纤维增强外层的情况下,例如,芯材料的树脂吸附以及实际的外层和夹层芯对总重量有所贡献。然而,根据本发明制造的模制品或本发明的板材可减少树脂吸附,这可以节省重量和成本。
根据本发明制造的模制品或板材的另一个优点被认为是,使用含发泡剂的泡沫和相关产品使得在模制品表面上并入一体化结构例如槽或孔并进一步处理模制品变得相对简单。在使用这种模制品(芯材料)的情况下,常将这种结构引入例如弯曲结构中(深槽)以用于包模(draping),以通过液体树脂工艺例如真空灌注提高加工性(孔),和用于加速所提及的加工操作(浅槽)。
对于制造本发明的板材而言,当模制品具有最低比例的挥发性成分以及尤其是仍存在的发泡剂时也是有利的。将纤维引入至泡沫中而获得模制品可以导致局部地在与树脂体系接触的所有位置处发泡剂的量非常迅速而显著地减少。这减少或防止了由于气体或发泡剂的夹杂而导致的层压板中的缺陷,并且改善了品质和/或机械性能。
纤维的引入另外导致因树脂体系的放热反应而引起的热分布更好。这减小了板材上侧和下侧之间的热梯度。同时,热量更好地分布在模制品体积中。具体地,对于具有低热稳定性的泡沫,这产生了优点。
通过将纤维相对于含发泡剂的泡沫的厚度方向(d)以0°至60°、更优选0°至45°的角度α引入至含发泡剂的泡沫中,可以获得进一步的改进/优点。通常,以0°至<90°的角度α引入纤维可在工业上进行。
当纤维不仅以平行的方式被引入至含发泡剂的泡沫中,而且另外的纤维还以相对于彼此优选为>0至180°的角度β引入时,可以获得另外的改进/优点。这另外实现了本发明的模制品在机械性能上的改进。
当本发明的板材中的(外部)树脂层是通过液体注入方法或液体灌注方法施加时,同样是有利的,其中纤维可在加工过程中用树脂浸渍并使机械性能得到改善。此外,可以节省成本。
下文中,进一步详述本发明。
根据本发明,在制造包含至少一个纤维(F)的模制品的方法中,将至少一个纤维(F)引入至由含发泡剂的泡沫制成的模制品中。
通常,含发泡剂的泡沫包含至少一种发泡剂和一种泡沫。泡沫可基于本领域技术人员已知的任何聚合物。
例如,含发泡剂的泡沫这样的泡沫基于至少一种选自聚苯乙烯、聚酯、聚苯醚、由苯醚制备的共聚物、由苯乙烯制备的共聚物、聚芳基醚砜、聚苯硫醚、聚芳基醚酮、聚丙烯、聚乙烯、聚酰胺、聚酰胺酰亚胺、聚醚酰亚胺、聚碳酸酯、聚丙烯酸酯、聚乳酸、聚氯乙烯或其混合物的聚合物,聚合物优选地选自聚苯乙烯、聚苯醚、聚苯乙烯和聚苯醚的混合物、聚对苯二甲酸乙二醇酯、聚碳酸酯、聚醚砜、聚砜、聚醚酰亚胺、由苯乙烯制备的共聚物、或由苯乙烯制备的共聚物的混合物,聚合物更优选为聚苯乙烯、聚苯乙烯和聚(2,6-二甲基苯醚)的混合物、苯乙烯-马来酸酐聚合物和苯乙烯-丙烯腈聚合物的混合物、或苯乙烯-马来酸酐聚合物(SMA)。
热塑性弹性体也适合作为泡沫。热塑性弹性体本身是本领域技术人员已知的。
聚苯醚优选为聚(2,6-二甲基亚苯基醚),其也被称为聚(2,6-二甲基苯醚)。
由亚苯基制备的合适的共聚物是本领域技术人员已知的。用于苯醚的合适的共聚单体也是本领域技术人员已知的。
由苯乙烯制备的共聚物优选具有选自以下的单体作为苯乙烯的共聚单体:α-甲基苯乙烯、环上卤代苯乙烯、环上烷基化苯乙烯、丙烯腈、丙烯酸酯、甲基丙烯酸酯、N-乙烯基化合物、马来酸酐、丁二烯、二乙烯基苯和丁二醇二丙烯酸酯。
含发泡剂的泡沫包含至少一种发泡剂。其可以包含恰好一种发泡剂或两种或更多种发泡剂。含发泡剂的泡沫包含在制造时的最大发泡剂含量。“在制造时”意指泡沫即将发泡之前,即该至少一种发泡剂即将脱附之前。换言之,在挤出泡沫的情况下,即将离开模口之前。在泡沫发泡期间,由于扩散操作,该至少一种发泡剂扩散出来,特别是在其制造之后从泡沫中扩散出来。在制造时的最大发泡剂含量通常为1重量%至15重量%,优选2重量%至10重量%,特别优选3重量%至8重量%的该至少一种发泡剂,基于含发泡剂的泡沫的总重量计。
在含发泡剂的泡沫中,发泡剂与泡沫的重量比取决于多种因素,例如发泡剂、发泡结构、泡沫聚合物、储存条件和制造过程中的接合点。
合适的发泡剂本身是本领域技术人员已知的,并且选自例如二氧化碳,烷烃如丙烷、异丁烷和戊烷,醇如甲醇、1-丙醇、2-丙醇、1-丁醇、2-丁醇、2-甲基丙醇和叔丁醇,醚如二甲醚,酮如丙酮或甲基乙基酮,卤代烃如氢氟丙烯,水,氮气以及它们的混合物。
优选地,本发明方法中的含发泡剂的泡沫中的至少一种发泡剂满足以下选项中的至少一个:
i)含发泡剂的泡沫中的至少一种发泡剂在标准压力下沸点为至少20℃,优选至少35℃,特别优选至少60℃,和/或
ii)含发泡剂的泡沫中的至少一种发泡剂为具有至少30g/mol、优选至少45g/mol、更优选至少55g/mol的分子量的有机发泡剂。
优选地,含发泡剂的泡沫中的所有发泡剂满足上述两个选项中的至少一个。
含发泡剂的泡沫中的至少一种发泡剂的沸点不高于400℃,优选不高于350℃,特别优选不高于300℃。
因此,含发泡剂的泡沫中的至少一种发泡剂,优选每种发泡剂具有例如20~400℃的沸点,优选为35~350℃,特别优选为60~200℃。
在另一个实施方案中,含发泡剂的泡沫中的至少一种发泡剂的沸点为-200℃~200℃,优选-100℃~150℃,特别优选-80℃~120℃。
在每种情况下,该至少一种发泡剂的沸点为基于在标准压力,即1013mbar下的沸点。
该至少一种发泡剂优选为具有200g/mol以下、优选180g/mol以下、特别优选150g/mol以下、尤其是100g/mol以下的分子量的有机发泡剂。
因此,含发泡剂的泡沫中的至少一种发泡剂,优选每种发泡剂优选为具有30~200g/mol、优选45~180g/mol、更优选55~150g/mol、最优选55~100g/mol的分子量的有机发泡剂。
通常,含发泡剂的泡沫中的至少一种发泡剂为具有16~250g/mol、更优选30~200g/mol、特别优选46~180g/mol的分子量的有机发泡剂。
有机发泡剂本身是本领域技术人员已知的;例如,有机发泡剂选自烷烃如丙烷、异丁烷和戊烷,醇如甲醇、1-丙醇、2-丙醇、1-丁醇、2-丁醇、2-甲基丙醇和叔丁醇,醚如二甲醚,酮如丙酮或甲基乙基酮,卤代烃如氢氟丙烯。
更优选地,上述关于沸点和分子量的细节适用于含发泡剂的泡沫中的所有发泡剂。
例如,含发泡剂的泡沫中的至少一种发泡剂,优选每种发泡剂选自六氟化硫、水、乙烷、正丙烷、正丁烷、正戊烷、正庚烷、异戊烷、环戊烷、环己烷、乙醇、丙醇、丙酮、甲基乙基酮、乙酸甲酯、乙酸乙酯、二甲醚、正己烷、正庚烷、呋喃、四氢呋喃、甲基丙基醚、异丁烷、甲醇、叔丁醇。
优选地,含发泡剂的泡沫中的至少一种发泡剂,优选每种发泡剂选自乙烷、正丙烷、正丁烷、正戊烷、正庚烷、异戊烷、环戊烷、环己烷、乙醇、丙醇、丙酮、甲基乙基酮、乙酸甲酯、乙酸乙酯、二甲醚、正己烷、正庚烷、呋喃、四氢呋喃、甲基丙基醚、异丁烷、甲醇、叔丁醇。
更优选地,含发泡剂的泡沫中的至少一种发泡剂,优选每种发泡剂选自乙烷、正丙烷、正丁烷、正戊烷、正庚烷、异戊烷、环戊烷、环己烷、乙醇、丙醇、丙酮、甲基乙基酮、乙酸甲酯、乙酸乙酯、正己烷、正庚烷、呋喃、四氢呋喃、甲基丙基醚、甲醇和叔丁醇。
还优选的是,含发泡剂的泡沫中的发泡剂都不是卤代烃。
用于制造含发泡剂的泡沫的方法本身是本领域技术人员已知的。例如,含发泡剂的泡沫可以珠粒发泡法、挤出发泡法、反应性发泡法和/或母料发泡法制造。
在这种情况下,含发泡剂的泡沫为例如模制泡沫、挤出泡沫、反应性泡沫和/或母料泡沫。优选地,含发泡剂的泡沫为挤出泡沫。更特别地,含发泡剂的泡沫为以包括以下步骤的方法制造的挤出泡沫:
I)在挤出机中提供聚合物熔体,
II)将至少一种发泡剂引入至步骤I)中提供的聚合物熔体中,获得可发泡聚合物熔体,
III)将步骤II)中获得的可发泡聚合物熔体从挤出机通过至少一个模口挤出到较低压力的区域中,并使可发泡聚合物熔体发泡,得到发泡泡沫,
IV)通过引导发泡泡沫通过成形工具来校正来自步骤III)的发泡泡沫,获得挤出泡沫,
V)对在步骤IV)中获得的挤出泡沫任选进行材料去除处理,
其中
i)步骤I)中提供的聚合物熔体任选地包含至少一种添加剂,和/或
ii)任选地将至少一种添加剂在步骤II)期间加入到聚合物熔体中,和/或在步骤II)和步骤III)之间加入到可发泡聚合物熔体中,和/或
iii)任选地将至少一种添加剂在步骤III)期间施用至发泡泡沫和/或在步骤IV)期间施用至发泡泡沫,和/或
iv)任选地将至少一个层(S2)在步骤IV)期间和/或在步骤IV)之后立刻施加到挤出泡沫上。
步骤I)中在挤出机中提供聚合物熔体的合适方法原则上为本领域技术人员已知的所有方法;例如,可通过熔化已经预聚合的聚合物而在挤出机中提供聚合物熔体。聚合物可在挤出机中直接熔融;同样可将聚合物以熔融形式进料至挤出机中,从而在步骤I)中在挤出机中提供聚合物熔体。同样可能的是在步骤I)中提供聚合物熔体,因为制备聚合物熔体的聚合物所需的相应单体在挤出机中彼此反应而形成聚合物,从而提供聚合物熔体。
在本文中,聚合物熔体应理解为意指在半结晶聚合物的情况下聚合物高于熔融温度(TM),或在无定形聚合物的情况下高于玻璃化转变温度(TG)。
通常,方法步骤I)中的聚合物熔体的温度为100~450℃,优选150~350℃,特别优选160~300℃。
在步骤II)中,将至少一种发泡剂引入至步骤I)中提供的聚合物熔体中。为此目的的方法本身是本领域技术人员已知的。
上述细节和优选适用于发泡剂。
在步骤II)中,由此获得可发泡聚合物熔体。可发泡聚合物熔体通常包含1~15重量%的至少一种发泡剂,优选为2~10重量%,特别优选3~8重量%,每种情况下基于可发泡聚合物熔体的总重量计。
在步骤II)中,挤出机中的压力通常为20~500巴,优选50~400巴,特别优选60~300巴。
在步骤III)中,将步骤II)中获得的可发泡聚合物熔体从挤出机通过至少一个模口挤出到较低压力的区域中,并使可发泡聚合物熔体发泡,获得发泡泡沫。
可发泡聚合物熔体的挤出方法本身是本领域技术人员已知的。
用于挤出可发泡聚合物熔体的合适的模口为本领域技术人员已知的那些。模口可具有任何期望的形状;例如,其可为矩形、圆形、椭圆形、正方形或六边形。优选矩形槽模和圆形圆模。
在一个实施方案中,可发泡聚合物熔体通过恰好一个模口、优选通过槽模挤出。在另一个实施方案中,可发泡聚合物熔体通过多个模口、优选圆形或六边形模口挤出而获得多个股(strand),多个股在从模口出现后立即结合而形成发泡泡沫。多个股也可仅在步骤IV)中通过穿过成形工具而结合。
优选地,将至少一个模口加热。特别优选地,当聚合物为无定形聚合物时,将模口至少加热到存在于步骤I)中提供的聚合物熔体中的聚合物的玻璃化转变温度(TG),并且当聚合物为半结晶聚合物时,将模口至少加热到存在于步骤I)中提供的聚合物熔体中的聚合物的熔融温度(TM);例如,模口的温度为80~400℃,优选为100~350℃,特别优选为110~300℃。
在步骤III)中,将可发泡聚合物熔体挤出至较低压力的区域。较低压力区域内的压力通常为0.05~5巴,优选0.5~1.5巴。
在步骤III)中,将可发泡聚合物熔体挤出模口的压力通常为20~600巴,优选40~300巴,特别优选50~250巴。
在步骤IV)中,通过引导发泡泡沫通过成形工具来校正来自步骤III)的发泡泡沫,获得挤出泡沫。
发泡泡沫的校正决定了步骤IV)中获得的挤出泡沫的外形。校正方法本身是本领域技术人员已知的。
成形工具可以直接设置在模口处。同样可能的是,成形工具设置在离模口一定距离处。
用于校正发泡泡沫的成形工具本身是本领域技术人员已知的。合适的成型工具包括例如片材校正设备、引取轮(roller takeoff)、芯杆校正设备、引取链和引取带。为了降低工具和挤出泡沫之间的摩擦系数,成形工具可以被涂覆或加热。
因此,步骤IV)中的校正固定本发明的挤出泡沫的横截面几何形状。优选地,挤出泡沫在至少一个维度上具有正交的横截面。如果校正仅在特定方向上部分地进行,则挤出泡沫可在自由表面处偏离理想的几何形状。挤出泡沫的厚度首先由模口决定,其次也由成形工具决定;这同样适用于挤出泡沫的宽度。
在步骤V)中,对步骤IV)中获得的挤出泡沫合适的材料去除处理方法原则上为本领域技术人员已知的所有方法。例如,挤出泡沫可通过锯削、铣削、钻销或刨削进行材料去除处理。
基于正交坐标系,将含发泡剂的泡沫的长度称为x方向,宽度称为y方向,厚度称为z方向。当通过挤出来制造挤出泡沫时,x方向对应于挤出泡沫的挤出方向。
可存在于步骤I)中的聚合物熔体中和/或可在步骤II)、III)或IV)期间加入和/或施用至发泡泡沫中的合适的添加剂原则上为本领域技术人员已知的任何添加剂,例如成核剂、阻燃剂、染料、加工稳定剂、加工助剂、光稳定剂和颜料。
关于在一个实施方案中在步骤IV)期间和/或之后施加于挤出泡沫的层(S2),可适用下面进一步描述的细节和优选。
根据本发明,将至少一个纤维(F)引入模制品中。
引入模制品中的纤维(F)为单个纤维或纤维束,优选纤维束。合适的纤维(F)为本领域技术人员已知能够形成纤维的所有材料。例如,纤维(F)为有机纤维、无机纤维、金属纤维或陶瓷纤维或其组合,优选聚合物纤维、玄武岩纤维、玻璃纤维、碳纤维或天然纤维,特别优选聚芳酰胺纤维、玻璃纤维、玄武岩纤维或碳纤维;聚合物纤维优选为聚酯、聚酰胺、聚芳酰胺、聚乙烯、聚氨酯、聚氯乙烯、聚酰亚胺和/或聚酰胺酰亚胺的纤维;天然纤维优选为剑麻、大麻、亚麻、竹子、椰子和/或黄麻的纤维。
在一个实施方案中,使用纤维束。纤维束由若干单个纤维(单纤维(filament))组成。每束的单个纤维的数量例如在玻璃纤维的情况下为至少10,优选为100至100 000,更优选为300至10 000,而在碳纤维的情况下为1000至50 000,并且特别优选在玻璃纤维的情况下为500至5000,而在碳纤维的情况下为2000至20 000。
根据本发明,至少一个纤维(F)在模制品内以纤维区域(FB2)存在并被含发泡剂的泡沫包围,而纤维(F)的纤维区域(FB1)从模制品的第一侧突出并且纤维(F)的纤维区域(FB3)从模制品的第二侧突出。
纤维区域(FB1)、纤维区域(FB2)和纤维区域(FB3)可各自占纤维(F)的总长度的任何所需比例。在一个实施方案中,纤维区域(FB1)和纤维区域(FB3)各自独立地占纤维(F)的总长度的1%至45%,优选2%至40%,更优选5%至30%,并且纤维区域(FB2)占纤维(F)的总长度的10%至98%,优选20%至96%,更优选40%至90%。
在另一个优选实施方案中,纤维(F)的纤维区域(FB1)突出的模制品的第一侧与纤维(F)的纤维区域(FB3)突出的模制品的第二侧相对。
优选地,将纤维(F)相对于模制品的厚度方向(d)或模制品的第一侧(的表面)的正交线以角度α引入至模制品中。角度α可采取从0°至90°的任何值。例如,将纤维(F)相对于模制品的厚度方向(d)以0°至60°的角度α引入至含发泡剂的泡沫中,优选0°至50°,更优选0°至15°或10°至70°,优选30°至60°,更优选30°至50°,甚至更优选30°至45°,特别是45°。
在另一个实施方案中,将至少两个纤维(F)以两个不同的角度α即α1和α2引入,其中角度α1优选为0°至15°,第二角度α2优选为30°至50°;特别优选α1为0°至5°,α2为40°至50°。优选地,本发明的模制品中所有的纤维(F)具有相同的角度α或至少大致相同的角度(相差不超过+/-5°,优选+/-2°,更优选+/-1°)。
优选地,本发明的模制品包含多个纤维(F),优选纤维束,和/或包含每m2超过10个纤维(F)或纤维束,优选每m2超过1000个,更优选每m2 4000至40 000个。
所有纤维(F)可在模制品中彼此平行地存在。根据本发明,同样可能和优选的是,两个或更多个纤维(F)在模制品中彼此成角度β而存在。角度β在本发明的上下文中应理解为意指第一纤维(F1)在模制品的第一侧表面上的正交投影与第二纤维(F2)在模制品表面上的正交投影之间的角度,两个纤维均已被引入至模制品中。
角度β优选在β=360°/n的范围内,其中n为整数。优选地,n为2~6,更优选2~4。例如,角度β为90°、120°或180°。在另一个实施方案中,角度β为80°~100°、110°~130°或170°~190°。在另一个实施方案中,将多于两个纤维(F)以彼此成角度β而引入,例如三个或四个纤维(F)。这三个或四个纤维(F)可各自具有相对于两个相邻纤维的两个不同角度β即β1和β2。优选地,所有的纤维(F)相对于两个相邻纤维(F)具有相同的角度β=β1=β2。例如,角度β为90°,在这种情况下,第一纤维(F1)与第二纤维(F2)之间的角度β1为90°,第二纤维(F2)与第三纤维(F3)之间的角度β2为90°,第三纤维与第四纤维(F4)之间的角度β3为90°,而第四纤维(F4)与第一纤维(F1)之间的角度β4同样为90°。那么,第一纤维(F1)(参照)与第二纤维(F2)、第三纤维(F3)和第四纤维(F4)之间的角度β在顺时针方向上为90°、180°和270°。类似的考虑适用于其他可能的角度。
在这种情况下,第一纤维(F1)具有第一方向,相对于第一纤维(F1)以角度β布置的第二纤维(F2)具有第二方向。优选地,在第一方向和第二方向上存在相似数量的纤维。在本上下文中,“相似”应理解为意指在相对于另一方向的每个方向上的纤维数之间的差异为<30%,更优选<10%,特别优选<2%。
纤维(F)或纤维束可以不规则或规则的样式引入。优选以规则的样式引入纤维或纤维束。在本发明的上下文中,“规则的样式”应理解为意指所有纤维彼此平行排列,并且至少一个纤维或纤维束具有与所有直接相邻的纤维或纤维束相同的距离(a)。特别优选地,所有纤维或纤维束具有与所有直接相邻的纤维或纤维束相同的距离。
在另一个优选的实施方案中,引入纤维(F)或纤维束,使得它们基于厚度方向(d)对应于z方向的正交坐标系,各自在x方向上具有彼此相同的距离(ax),并且在y方向上具有相同的距离(ay)。特别优选地,它们在x方向和y方向上具有相同的距离(a),其中a=ax=ay
如果两个以上的纤维(F)彼此成角度β,则彼此平行的第一纤维(F1)优选具有第一距离(a1)的规则的样式,而彼此平行并且与第一纤维(F1)成角度β的第二纤维(F2)优选具有第二距离(a2)的规则的样式。在优选的实施方案中,第一纤维(F1)和第二纤维(F2)各自具有距离(a)的规则的样式。在这种情况下,a=a1=a2
如果将纤维或纤维束彼此成角度β引入至泡沫中,则优选纤维或纤维束在每个方向上遵循规则的样式。
图1示出了根据本发明制造的由含发泡剂的泡沫(1)制成的模制品的优选实施方案的透视图的示意图。(2)表示模制品的第一侧(的表面),而(3)表示相应模制品的第二侧。从图1还可看出,模制品的第一侧(2)与该模制品的第二侧(3)相对。纤维(F)由(4)表示。该纤维的一端(4a)及纤维区域(FB1)从模制品的第一侧(2)突出,而构成纤维区域(FB3)的纤维另一端(4b)从模制品的第二侧(3)突出。中间纤维区域(FB2)在模制品内,因此被泡沫包围。
在图1中,例如为单个纤维或纤维束(优选纤维束)的纤维(4)相对于模制品的厚度方向(d)或模制品的第一侧(2)(的表面)的正交线成角度α。角度α可采用0°至90°的任何值,通常为0°至60°,优选为0°至50°,更优选为0°至15°或10°至70°,优选为30°至60°,更优选为30°至50°,非常特别为30°至45°,尤其是45°。为清楚起见,图1仅示出单个纤维(F)。
图3以示例方式示出了一些不同角度的示意图。图3中所示的由含发泡剂的泡沫(1)制成的模制品包含第一纤维(41)和第二纤维(42)。在图3中,为了更加清楚,对于两个纤维(41)和(42),仅示出了从模制品的第一侧(2)突出的纤维区域(FB1)。第一纤维(41)相对于模制品的第一侧(2)表面的正交线(O)形成第一角度α(α1)。第二纤维(42)相对于第一侧(2)表面的正交线(O)形成第二角度α(α2)。第一纤维(41)在模制品的第一侧(2)上的正交投影(41p)与第二纤维(42)在模制品的第一侧(2)上的正交投影(42p)形成角度β。
用于制造包含至少一个纤维(F)的模制品的合适方法原则上包括本领域技术人员已知的所有方法。合适的方法记载于例如WO 2006/125561或WO 2011/012587中。
例如,在本发明的方法中,通过使用针缝入而将至少一个纤维(F)部分地引入至含发泡剂的泡沫中,优选通过步骤a)至f)进行部分引入:
a)任选地将至少一个层(S2)施加到含发泡剂的泡沫的至少一侧上,
b)在含发泡剂的泡沫和任何层(S2)中,对应于每个纤维(F)产生一个孔,该孔从含发泡剂的泡沫的第一侧延伸至第二侧并且穿过任何层(S2),
c)在含发泡剂的泡沫的第二侧上提供至少一个纤维(F),
d)使针从含发泡剂的泡沫的第一侧通过孔穿到含发泡剂的泡沫的第二侧,并使针穿过任何层(S2),
e)将至少一个纤维(F)固定在含发泡剂的泡沫的第二侧上的针上,
f)将针与纤维(F)一起通过孔返回,使得纤维(F)在模制品内以纤维区域(FB2)存在并被泡沫包围,而纤维(F)的纤维区域(FB1)从模制品的第一侧或从任何层(S2)突出并且纤维(F)的纤维区域(FB3)从模制品的第二侧突出,
更优选同时进行步骤b)和d)。
步骤a)中至少一个层(S2)的施加可例如如上文所述地在步骤IV)期间和/或在步骤IV)之后立刻进行。
在特别优选的实施方案中,步骤b)和d)同时进行。在该实施方案中,通过将针从含发泡剂的泡沫的第一侧穿到含发泡剂的泡沫的第二侧,产生含发泡剂的泡沫的从第一侧到第二侧的孔。
在该实施方案中,至少一个纤维(F)的引入可以包括例如以下步骤:
a)任选地将层(S2)施加到含发泡剂的泡沫的至少一侧上,
b)在含发泡剂的泡沫的第二侧上提供至少一个纤维(F),
c)在含发泡剂的泡沫和任何层(S2)中,对应于每个纤维(F)产生一个孔,该孔从含发泡剂的泡沫的第一侧延伸至第二侧并且穿过任何层(S2),通过将针穿过含发泡剂的泡沫并穿过任何层(S2)而产生所述孔,
d)将至少一个纤维(F)固定在含发泡剂的泡沫的第二侧上的针上,
e)将针与纤维(F)一起通过孔返回,使得纤维(F)在模制品内以纤维区域(FB2)存在并被含发泡剂的泡沫包围,而纤维(F)的纤维区域(FB1)从模制品的第一侧或从任何层(S2)突出并且纤维区域(FB3)从模制品的第二侧突出,
f)任选地在第二侧上切断纤维(F),
g)任选地切开纤维(F)在针上形成的线圈。
在优选的实施方案中,使用的针为钩针,并且在步骤d)中,至少一个纤维(F)被钩在钩针中。
在另一个优选实施方案中,按照上述步骤将多个纤维(F)同时引入至含发泡剂的泡沫中。
本发明的方法优选在部分引入至少一个纤维(F)时,模制品的含发泡剂的泡沫仍包含至少5重量%、优选至少10重量%、更优选至少25重量%、最优选至少50重量%的量的至少一种发泡剂(优选所有发泡剂)时进行,基于用于制造含发泡剂的泡沫的至少一种发泡剂(优选所有发泡剂)的量计。
本发明的方法也优选在部分引入至少一个纤维(F)时,模制品的含发泡剂的泡沫仍包含不超过100重量%、优选不超过99重量%且更优选不超过95重量%的量的至少一种发泡剂(优选所有发泡剂)时进行,基于用于制造含发泡剂的泡沫的至少一种发泡剂(优选所有发泡剂)的量计。
“所有发泡剂的量”基于存在于含发泡剂的泡沫中的所有发泡剂计。因此,如果含发泡剂的泡沫包含恰好一种发泡剂,则发泡剂的量基于恰好一种发泡剂计。相反,如果含发泡剂的泡沫包含两种或更多种发泡剂,则发泡剂的量基于两种或更多种发泡剂计。
有若干种方法可用于测定发泡剂含量。若所用泡沫具有足够的热稳定性,可通过热重分析(TGA)加热泡沫直至所有发泡剂脱附结束。然后,质量的损失对应于仍存在于泡沫中的发泡剂的量。
对于各种发泡剂的分析,可以使用以下方法,例如:对于各种有机发泡剂的分析,可以采用例如顶空气相色谱法。将样品溶解在溶剂中,并通过定量色谱法确定发泡剂的量和类型。用于此目的的方法是本领域技术人员已知的。在使用水作为发泡剂的情况下,可通过卡尔·费歇尔库仑滴定法来测定水的含量。
本发明的方法也优选在部分引入至少一个纤维(F)时,模制品的含发泡剂的泡沫仍包含大于20重量%、优选大于50重量%、特别优选大于70重量%的至少一种发泡剂时进行,基于含发泡剂的泡沫完成时存在于含发泡剂的泡沫中的至少一种发泡剂的量计。
本发明的方法也优选在部分引入至少一个纤维(F)时,模制品的含发泡剂的泡沫仍包含不超过100重量%、优选不超过99重量%且更优选不超过95重量%的量的至少一种发泡剂时进行,基于含发泡剂的泡沫完成时存在于含发泡剂的泡沫中的至少一种发泡剂的量计。
如果泡沫中存在多于一种发泡剂,则这意味着这些发泡剂中的至少一种仍以大于20重量%、优选大于50重量%、特别优选大于70重量%的程度存在。其他的发泡剂也可以较少的量存在。
进一步优选的是,将至少一个纤维(F)部分引入至含发泡剂的泡沫中是在基于含发泡剂的泡沫完成的时刻计不迟于十二周后进行,优选不迟于六周后,更优选不迟于三周后,尤其是48小时,特别是不迟于2小时后。
进一步优选的是,无关于发泡剂的量,将至少一个纤维(F)部分引入至含发泡剂的泡沫中是在稳定化时间结束之前进行,优选不迟于稳定化时间经过一半后,更优选不迟于稳定化时间经过四分之一后,基于直接得到的泡沫的稳定化时间计。
优选地,本发明的方法还满足以下选项中的至少一个:
i)与不含纤维的含发泡剂的泡沫相比,作为引入纤维(F)的结果,模制品的含发泡剂的泡沫中的至少一种发泡剂(优选模制品的含发泡剂的泡沫中的所有发泡剂)的脱附增加至至少1.2倍,优选至少1.5倍,更优选至少2.0倍,特别优选至少3.0倍,和/或
ii)与不含纤维的含发泡剂的泡沫相比,作为引入至少一个纤维(F)的结果,含发泡剂的泡沫的稳定化时间以至少1.2的系数减少,优选至少1.5,更优选至少2.0,特别优选至少3.0。
通常,与不含纤维的含发泡剂的泡沫相比,作为引入纤维(F)的结果,模制品的含发泡剂的泡沫中的至少一种发泡剂(优选模制品的含发泡剂的泡沫中的所有发泡剂)的脱附增加至不超过10 000 000倍,优选不超过100 000倍,更优选不超过1000倍,特别优选不超过100倍。
在本上下文中,“至少一种发泡剂的脱附”应理解为意指存在于含发泡剂的泡沫中的至少一种发泡剂与来自环境的空气的交换。作为至少一种发泡剂脱附的结果,泡沫中存在的该至少一种发泡剂因而被空气所替代,使得含发泡剂的泡沫包含越来越少的发泡剂和更多的空气。
通过上述发泡剂分析方法来测量至少一种发泡剂的脱附。为此,在制造模制品之前测定泡沫的发泡剂含量。随后处理泡沫的一部分以得到本发明的模制品;另一部分储存在相同的环境条件下作为参照样品。在各别的时间段后测定两个泡沫中发泡剂的量。这显示出与未处理的参照样品相比,根据本发明的模制品明显更快速地脱附。为了评估升高的脱附因子,需在引入纤维(F)后的前两周内进行测量。所述因子基于此期间内的任何时刻计。
通常,与不含纤维的含发泡剂的泡沫相比,作为引入至少一个纤维(F)的结果,含发泡剂的泡沫的稳定化时间以不超过1000的系数减少,优选不超过500,更优选不超过200,特别优选不超过100。
稳定化时间应理解为意指在泡沫的制造与泡沫在热应力下尺寸足够稳定所需的最早时刻之间的时间段。在泡沫的后续处理或使用温度下,泡沫的几何尺寸通常必须保持几乎恒定。例如,厚度、长度和宽度都不能出现任何显著的变化。此外,应避免其他变形,如局部或整体的缩痕、凸起和塌陷。
为了测定尺寸稳定性,将规定尺寸的泡沫(例如宽度为500mm、长度为1m的板坯)在恒温的加热箱中储存数小时(例如数小时至数天)。随后,测定板坯的几何形状并将其与加热储存之前的状态进行比较。在许多情况下,例如,不同空间方向的尺寸变化超过3%是不允许的;此外,应避免凸起和缩痕。确切的条件取决于泡沫或模制品后来的最终用途。
在所有情况下,稳定化时间描述泡沫制造后达到充分稳定所需的时间段。根据发泡剂发泡泡沫的密度、厚度、结构和配方,该时间段可在几秒到几个月的范围内变化。在使用对泡沫施加塑化作用的有机发泡剂的情况下尤其如此。
本发明还提供通过本发明的方法制造的模制品。
本发明还提供一种包括至少一个根据本发明制造的模制品和至少一个层(S1)的板材。在某些情况下,“板材”在专业人员中也可能被称为“夹层物”、“夹层材料”、“层压板”和/或“复合制品”。
在板材的优选实施方案中,板材具有两个层(S1),并且两个层(S1)各自安置在模制品的与模制品中相应的另一侧相对的一侧上。
在本发明的板材的一个实施方案中,层(S1)包含至少一种树脂,所述树脂优选为反应性热固性树脂或热塑性树脂,该树脂更优选基于环氧化物、丙烯酸酯、聚氨酯、聚酰胺、聚酯、不饱和聚酯、乙烯基酯或其混合物,该树脂特别地为胺固化环氧树脂、潜在固化环氧树脂、酸酐固化环氧树脂或由异氰酸酯和多元醇形成的聚氨酯。这种树脂体系是本领域技术人员已知的,例如知于Penczek等(Advances in Polymer Science,184,p.1-95,2005)、Pham等(Ullmann's Encyclopedia of Industrial Chemistry,vol.13,2012)、Fahnler(Polyamide,Kunststoff Handbuch 3/4,1998)和Younes(WO12134878A2)。
根据本发明,还优选一种板材,其中
i)纤维(F)的纤维区域(FB1)与第一层(S1)部分或完全接触,优选完全接触,和/或
ii)纤维(F)的纤维区域(FB3)与第二层(S1)部分或完全接触,优选完全接触,和/或
iii)板材在模制品的至少一侧和至少一个层(S1)之间具有至少一个层(S2),层(S2)优选由二维纤维材料或聚合物膜构成,更优选由网、稀松布或织物形式的玻璃纤维或碳纤维构成。
在本发明的另一个板材实施方案中,至少一个层(S1)还包含至少一种纤维材料,其中
i)所述纤维材料包括以短切纤维、网、稀松布、编结物和/或织物的一个或多个薄层形式的纤维,优选以稀松布或织物的形式,更优选以每稀松布或织物的基重为150~2500g/m2的稀松布或织物的形式,和/或
ii)所述纤维材料包括有机、无机、金属或陶瓷纤维的纤维,优选聚合物纤维、玄武岩纤维、玻璃纤维、碳纤维或天然纤维,更优选玻璃纤维或碳纤维。
上述细节可适用于天然纤维和聚合物纤维。
另外包含至少一种纤维材料的层(S1)也被称为纤维增强层,如果层(S1)包含树脂,则尤其称为纤维增强树脂层。
图2示出了本发明的另一优选实施方案。该图示出本发明的板材(7)的二维侧视图,其包括如上(例如图1实施方案的上下文中)所述的根据本发明制造的模制品(1)。除非另有说明,在图1和图2中的其它缩写的情况下,附图标记具有相同的含义。
在根据图2的实施方案中,本发明的板材包括由(5)和(6)表示的两个层(S1)。两个层(5)和(6)分别位于模制品(1)的彼此相对的两侧上。两个层(5)和(6)优选为树脂层或纤维增强树脂层。从图2可进一步看出,纤维(4)的两端被相应的层(5)和(6)包围。
任选地,在模制品(1)与第一层(5)之间和/或模制品(1)与第二层(6)之间可存在一个或多个另外的层。如以上针对图1所述,为简化起见,图2也以(4)示出了单个纤维(F)。在实践中,关于纤维或纤维束的数量,类似的叙述适用于以上针对图1所述的那些。
本发明还提供一种制造本发明的板材的方法,其中将至少一个反应性粘性树脂形式的层(S1)施加于本发明的模制品并固化,优选通过液体浸渍方法,更优选通过压力或真空辅助浸渍方法,特别优选通过真空灌注或压力辅助注入方法,最优选通过真空灌注来进行。液体浸渍方法本身是本领域技术人员已知的,并详细记载于例如Wiley Encyclopediaof Composites(第2版,Wiley,2012)、Parnas等(Liquid Composite molding,Hanser,2000)和Williams等(Composite Part A,27,p.517-524,1997)中。
可以使用各种辅助材料来制造本发明的板材。适于通过真空灌注来制造的辅助材料为,例如优选由尼龙制成的真空膜,真空密封带,优选由尼龙制成的助流剂,优选由聚烯烃制成的分离膜,优选由聚酯制成的撕开式(tearoff)织物,和半透膜,优选为膜式膜(membrane film)、更优选为PTFE膜式膜,以及优选由聚酯制成的吸收性起绒布。对合适辅助材料的选择由待制造的部件、选择的工艺和使用的材料特别是树脂体系来指导。在使用基于环氧化物和聚氨酯的树脂体系的情况下,优选使用由尼龙制成的助流剂、由聚烯烃制成的分离膜、由聚酯制成的撕开式织物和作为PTFE膜式膜的半透膜,以及由聚酯制成的吸收性起绒布。
在本发明的制造板材的方法中,这些辅助材料可以多种方式来使用。更优选通过真空灌注施加纤维增强外层而由模制品制造板材。在典型的结构中,为制造本发明的板材,将纤维材料和任选的其它层施加至模制品的上侧和下侧。随后,放置撕开式织物和分离膜。在液体树脂体系的灌注中,可使用助流剂和/或膜式膜。特别优选以下变化:
i)在结构的仅一侧上使用助流剂,和/或
ii)在结构的两侧上使用助流剂,和/或
iii)如下的结构,其具有半透膜(VAP构造);后者优选包覆在模制品的整个区域上,在模制品的一侧或两侧上使用助流剂、分离膜和撕开式织物,并且通过真空密封带将半透膜相对于模具表面密封,将吸收性起绒布插入远离模制品的半透膜一侧,其结果使得空气在整个区域上向上抽空,和/或
iv)使用由膜式膜制成的真空袋,其优选地位于模制品的开口(gate)相对侧,通过其将空气从开口的相对侧抽空。
该结构随后配备了用于树脂体系的开口和用于抽空的开口。最后,将真空膜施加在整个结构上并用密封带密封,并且将整个结构抽真空。在灌注树脂体系之后,树脂体系的反应在保持真空的情况下进行。
本发明还提供根据本发明制造的模制品或根据本发明制造的板材用于风力涡轮机中的转子叶片、运输行业、建筑行业、汽车构造、船舶制造、铁路车辆构造、集装箱构建、卫生设施和/或航空航天中的用途。

Claims (20)

1.一种用于制造包含至少一个纤维(F)的模制品的方法,其包括将至少一个纤维(F)部分地引入至由含发泡剂的泡沫制成的模制品内于所述含发泡剂的泡沫中,其结果是,纤维(F)在模制品内以纤维区域(FB2)存在并被含发泡剂的泡沫包围,而纤维(F)的纤维区域(FB1)从模制品的第一侧突出并且纤维(F)的纤维区域(FB3)从模制品的第二侧突出,其中所述模制品包含每m2超过1000个纤维(F),并且其中在部分引入至少一个纤维(F)时,模制品的含发泡剂的泡沫仍包含至少5重量%的量的至少一种发泡剂,基于用于制造含发泡剂的泡沫的至少一种发泡剂的量计。
2.根据权利要求1所述的方法,其中在部分引入至少一个纤维(F)时,模制品的含发泡剂的泡沫仍包含至少10重量%的至少一种发泡剂,基于用于制造含发泡剂的泡沫的至少一种发泡剂的量计。
3.根据权利要求1或2所述的方法,其中含发泡剂的泡沫中的至少一种发泡剂
i)在标准压力下沸点为至少20℃,和/或
ii)为具有至少30g/mol的分子量的有机发泡剂。
4.根据权利要求1或2所述的方法,其中
i)作为引入纤维(F)的结果,模制品的含发泡剂的泡沫中的至少一种发泡剂的脱附增加至至少1.2倍,和/或
ii)与不含纤维的含发泡剂的泡沫相比,作为引入至少一个纤维(F)的结果,含发泡剂的泡沫的稳定化时间以至少1.2的系数减少。
5.根据权利要求1或2所述的方法,其中含发泡剂的泡沫为模制泡沫、挤出泡沫、反应性泡沫或母料泡沫,其是以包括以下步骤的方法制造的:
I)在挤出机中提供聚合物熔体,
II)将至少一种发泡剂引入至步骤I)中提供的聚合物熔体中,获得可发泡聚合物熔体,
III)将步骤II)中获得的可发泡聚合物熔体从挤出机通过至少一个模口挤出到较低压力的区域中,并使可发泡聚合物熔体发泡,得到发泡泡沫,
IV)通过引导发泡泡沫通过成形工具来校正来自步骤III)的发泡泡沫,获得挤出泡沫,
V)对在步骤IV)中获得的挤出泡沫任选进行材料去除处理,
其中
i)步骤I)中提供的聚合物熔体任选地包含至少一种添加剂,或
ii)任选地将至少一种添加剂在步骤II)期间加入到聚合物熔体中,或在步骤II)和步骤III)之间加入到可发泡聚合物熔体中,或
iii)任选地将至少一种添加剂在步骤III)期间施用至发泡泡沫或在步骤IV)期间施用至发泡泡沫,或
iv)任选地将至少一个层(S2)在步骤IV)期间或在步骤IV)之后立即施加到挤出泡沫上。
6.根据权利要求1或2所述的方法,其中含发泡剂的泡沫基于至少一种选自聚苯乙烯、聚酯、聚苯醚、由苯醚制备的共聚物、由苯乙烯制备的共聚物、聚芳基醚砜、聚苯硫醚、聚芳基醚酮、聚丙烯、聚乙烯、聚酰胺、聚酰胺酰亚胺、聚醚酰亚胺、聚碳酸酯、聚丙烯酸酯、聚乳酸、聚氯乙烯、热塑性弹性体或其混合物的聚合物。
7.根据权利要求1或2所述的方法,其中
i)纤维(F)为单个纤维或纤维束,或
ii)纤维(F)为有机纤维或无机纤维,或
iii)纤维(F)以纤维束形式使用,所述纤维束每束的单个纤维的数量在玻璃纤维的情况下为至少10,而在碳纤维的情况下为1000至50000,或
iv)纤维区域(FB1)和纤维区域(FB3)各自独立地占纤维(F)的总长度的1%至45%,并且纤维区域(FB2)占纤维(F)的总长度的10%至98%。
8.根据权利要求7所述的方法,其中纤维(F)为金属纤维或陶瓷纤维。
9.根据权利要求1或2所述的方法,其中
i)将纤维(F)相对于模制品的厚度方向(d)以0°至60°或10°至70°的角度α引入至含发泡剂的泡沫中或
ii)在模制品中,有纤维(F)的纤维区域(FB1)突出的模制品的第一侧与有纤维(F)的纤维区域(FB3)突出的模制品的第二侧相对,或
iii)模制品包含每m2 4000至40 000个纤维(F)。
10.根据权利要求1或2所述的方法,其中通过使用针缝入而将至少一个纤维(F)部分地引入至含发泡剂的泡沫中,
通过步骤a)至f)进行部分引入:
a)任选地将至少一个层(S2)施加到含发泡剂的泡沫的至少一侧上,
b)在含发泡剂的泡沫和任何层(S2)中,对应于每个纤维(F)产生一个孔,该孔从含发泡剂的泡沫的第一侧延伸至第二侧并且穿过任何层(S2),
c)在含发泡剂的泡沫的第二侧上提供至少一个纤维(F),
d)使针从含发泡剂的泡沫的第一侧通过孔穿到含发泡剂的泡沫的第二侧,并使针穿过任何层(S2),
e)将至少一个纤维(F)固定在含发泡剂的泡沫的第二侧上的针上,
f)将针与纤维(F)一起通过孔返回,使得纤维(F)在模制品内以纤维区域(FB2)存在并被含发泡剂的泡沫包围,而纤维(F)的纤维区域(FB1)从模制品的第一侧或从任何层(S2)突出并且纤维(F)的纤维区域(FB3)从模制品的第二侧突出。
11.通过根据权利要求1所述的方法制造的模制品。
12.一种板材,其包括至少一个根据权利要求11所述的模制品和至少一个层(S1)。
13.根据权利要求12所述的板材,其中层(S1)包含至少一种树脂。
14.根据权利要求13所述的板材,其中所述树脂基于环氧化物、丙烯酸酯、聚氨酯、聚酰胺、聚酯、不饱和聚酯、乙烯基酯或其混合物。
15.根据权利要求12或13所述的板材,其中层(S1)还包含至少一种纤维材料,其中
i)所述纤维材料包括以短切纤维、网、稀松布、编结物或织物的一个或多个薄层形式的纤维,或
ii)所述纤维材料包括有机、无机、金属或陶瓷纤维。
16.根据权利要求12或13所述的板材,其中所述板材具有两个层(S1),并且两个层(S1)各自安置在模制品的与模制品中相应的另一侧相对的一侧上。
17.根据权利要求12或13所述的板材,其中
i)纤维(F)的纤维区域(FB1)与第一层(S1)部分或完全接触,或
ii)纤维(F)的纤维区域(FB3)与第二层(S1)部分或完全接触,或
iii)板材在模制品的至少一侧和至少一个层(S1)之间具有至少一个层(S2)。
18.根据权利要求17所述的板材,其中层(S2)由二维纤维材料或聚合物膜构成。
19.一种制造根据权利要求12所述的板材的方法,其包括在根据权利要求11所述的模制品上制备、施加和固化反应性粘性树脂形式的至少一个层(S1)。
20.根据权利要求11所述的模制品或根据权利要求12所述的板材用于风力涡轮机中的转子叶片、运输行业、建筑行业、汽车构造、船舶制造、铁路车辆构造、集装箱构建、卫生设施和/或航空航天中的用途。
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