CN107250228A - 由互相连接的片段组成的纤维增强泡沫材料 - Google Patents
由互相连接的片段组成的纤维增强泡沫材料 Download PDFInfo
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- CN107250228A CN107250228A CN201580076658.3A CN201580076658A CN107250228A CN 107250228 A CN107250228 A CN 107250228A CN 201580076658 A CN201580076658 A CN 201580076658A CN 107250228 A CN107250228 A CN 107250228A
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Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C70/00—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts
- B29C70/04—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts comprising reinforcements only, e.g. self-reinforcing plastics
- B29C70/06—Fibrous reinforcements only
- B29C70/08—Fibrous reinforcements only comprising combinations of different forms of fibrous reinforcements incorporated in matrix material, forming one or more layers, and with or without non-reinforced layers
- B29C70/086—Fibrous reinforcements only comprising combinations of different forms of fibrous reinforcements incorporated in matrix material, forming one or more layers, and with or without non-reinforced layers and with one or more layers of pure plastics material, e.g. foam layers
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C44/00—Shaping by internal pressure generated in the material, e.g. swelling or foaming ; Producing porous or cellular expanded plastics articles
- B29C44/34—Auxiliary operations
- B29C44/35—Component parts; Details or accessories
- B29C44/352—Means for giving the foam different characteristics in different directions
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- Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
Abstract
本发明涉及由泡沫材料制成的模制品,其中至少一根纤维(F)部分地在模制品内,即被泡沫材料包围。因此各个纤维(F)的未被泡沫包围的两端从相应模制品的一侧突出。所述泡沫材料包含至少两个相互连接的泡沫材料段。
Description
本发明涉及由泡沫制成的模制品,其中至少一根纤维(F)部分地在模制品内,即被泡沫包围。因此,各个纤维(F)的未被泡沫包围的两端分别从相应模制品的一侧突出。所述泡沫包含至少两个相互粘结的泡沫段。
本发明还提供一种包含至少一个所述模制品和至少一个其他层(S1)的面板。本发明还提供由泡沫制造本发明的模制品或本发明的面板的方法以及其用途,例如作为风力涡轮机中的转子叶片。
WO 2006/125561涉及一种制造增强多孔材料的方法,其中在第一方法步骤中,在多孔材料中产生至少一个从多孔材料的第一表面延伸到第二表面的孔。在多孔材料的第二表面的另一侧上,提供至少一个纤维束,所述纤维束用针牵引穿过孔至多孔材料的第一侧。然而,在针固定纤维束之前,首先将针拉动穿过来自多孔材料的第一侧的特定孔。此外,根据WO 2006/125561的方法的结论,纤维束部分地在多孔材料内,因为它填充了相应的孔,并且各侧上的相应纤维束部分地从多孔材料的第一和第二表面突出。
通过WO 2006/125561中记载的方法,可制造包含所述多孔材料的芯和至少一个纤维束的夹心状组件。可将树脂层和纤维增强树脂层施用到该芯的表面上,以制造实际的夹心状组件。用于形成夹心状组件的芯的多孔材料可为例如聚氯乙烯或聚氨酯。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没有公开包含至少两个相互粘结的泡沫段的泡沫也可被用作多孔材料用于制造夹心状组件中的芯。WO 2006/125561的夹心状组件适合用于飞机结构。
WO 2011/012587涉及另一种用于制造用于面板——由复合材料制成——的具有集成桥接纤维的芯的方法。该芯通过借助针牵引桥接纤维——在由轻质材料制成的被称为“饼状物(cake)”的表面上所提供——部分或完全地穿过所述饼状物而制成。“饼状物”可以由聚氨酯泡沫、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形成,特别是由聚氨酯泡沫形成。所使用的纤维原则上可为任何种类的单根或多根线状物和其他纱线。
由此制得的芯又可为由复合材料制成的面板的一部分,其中在夹层结构中,所述芯的一侧或两侧被树脂基质和树脂基质与纤维的组合物包围。然而,WO 2011/012587没有公开包含至少两个相互粘结的泡沫段的泡沫可被用于制造相应的芯材料。
WO 2012/138445涉及使用多个具有低密度的多孔材料的纵向长条来制造复合芯面板的方法。将双层纤维垫引入单个的长条之间,并且通过使用树脂使得单个长条粘结,以形成复合芯面板。根据WO 2012/138445,形成纵向长条的低密度的多孔材料选自轻木、弹性泡沫和纤维增强的复合泡沫。单个条带之间引入的双层形式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,或热活化的热塑性塑料,例如聚丙烯或PET。然而,WO 2012/138445没有公开可将单个的纤维或纤维束纳入多孔材料中用于增强。根据WO 2012/138445,在借助树脂粘合剂粘结单个长条以获得芯材料的上下文中,仅另外构成粘合元件的纤维垫被用于此目的。
GB-A 2 455 044公开了一种制造多层复合制品的方法,其中在第一方法步骤中,提供了许多热塑性材料的珠粒和发泡剂。所述热塑性材料是聚苯乙烯(PS)和聚苯醚(PPO)的混合物,其包含至少20重量%至70重量%的PPO。在第二方法步骤中,使珠粒膨胀,并且在第三步骤中,将它们焊接在模具中以形成热塑性材料的闭孔泡沫,以得到模制品,闭孔泡沫假定呈模具的形状。在下一方法步骤中,将纤维增强材料层施用到闭孔泡沫的表面,使用环氧树脂进行各个表面的连接。然而,GB-A 2 455044没有公开可将纤维材料引入到多层复合制品的芯中。
在WO 2009/047483中也公开了类似的方法和类似的多层复合制品(类似于GB-A 2455 044中的那些)。这些多层复合制品适合于例如用作转子叶片(在风力涡轮机中)或用作船的船体。
US-B 7,201,625公开了一种制造泡沫产品的方法以及该泡沫产品,其可以例如在运动领域中作为冲浪板使用。泡沫产品的芯通过模制泡沫形成,例如基于聚苯乙烯泡沫的模制泡沫。该模制泡沫在特定模具中制造,并且外部塑料外壳包围该模制泡沫。外部塑料外壳可例如为聚乙烯薄膜。然而,US-B 7,201,625也没有公开用于增强材料的纤维可存在于模制泡沫中。
US-B 6,767,623公开了具有模制聚丙烯泡沫的芯层的夹心面板,所述模制聚丙烯泡沫基于粒径为2至8mm且堆积密度为10至100g/L的颗粒。此外,该夹心面板还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,以形成夹心结构。为了装饰目的,其他的层也可以任选地存在于夹心面板中。所述外层可包含玻璃纤维或其他聚合物纤维。
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。这些挤出泡沫的显著特征是其改善的刚度。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并未描述挤出泡沫包含纤维或包含至少两个相互粘结的泡沫段。
WO 2005/056653涉及由包含填料的可膨胀聚合物珠粒形成的模制泡沫。该模制泡沫可通过焊接由包含填料的可膨胀热塑性聚合物珠粒所形成的预发泡泡沫珠粒而获得,该模塑泡沫的密度为8至300g/L。所述热塑性聚合物珠粒尤其包含苯乙烯聚合物。所用的填料可为粉状无机物质、金属、白垩、氢氧化铝、碳酸钙或氧化铝,或以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 2001/0031350记载了包含纤维增强的具有低密度的闭孔材料、增强纤维层和树脂的夹心材料。所述具有低密度的闭孔材料是泡沫。夹心材料的芯材料包含通过纤维层彼此粘结的泡沫段。此外,纤维——例如以粗纱的形式——可以被引入到所述段中用于增强,并且可以穿透纤维层。纤维在芯材料内存在有区域,并且第二纤维区域从泡沫的第一侧突出,且第三纤维区域从第二侧突出。为了将纤维引入到泡沫中,US 2001/0031350使用了针。针产生了从泡沫的第一侧到第二侧的孔,同时将纤维从泡沫的第一侧带到泡沫的第二侧,使得纤维部分在泡沫内且部分在泡沫外部。
本发明的目的在于提供新的纤维增强模制品或面板。
根据本发明,该目的通过由泡沫制成的模制品来实现,所述泡沫包含至少两个相互粘结的泡沫段,其中至少一根纤维(F)在模制品内存在有纤维区域(FB2)并被泡沫包围,同时纤维(F)的纤维区域(FB1)从模制品的第一侧突出,且纤维(F)的纤维区域(FB3)从模制品的第二侧突出,其中纤维(F)已经通过包括以下步骤a)至f)的方法部分地引入到泡沫中:
a)任选地将至少一层(S2)施用到泡沫的至少一侧,
b)对于每根纤维(F)在泡沫和任意层(S2)中产生一个孔,该孔从泡沫的第一侧延伸到第二侧并穿过任意层(S2),
c)在泡沫的第二侧上提供至少一根纤维(F),
d)使针从泡沫的第一侧穿过所述孔到泡沫的第二侧,并使针穿过任意层(S2),
e)在泡沫的第二侧上将至少一根纤维(F)固定在针上,以及
f)将针与纤维(F)一起通过孔返回,使得纤维(F)在模制品内存在有纤维区域(FB2)并被泡沫包围,同时纤维(F)的纤维区域(FB1)从模制品的第一侧或从任意层(S2)突出,且纤维(F)的纤维区域(FB3)从模制品的第二侧突出。
本发明还提供由泡沫制成的模制品,所述泡沫包含至少两个相互粘结的泡沫段,其中至少一根纤维(F)在模制品内存在有纤维区域(FB2)并被泡沫包围,同时纤维(F)的纤维区域(FB1)从模制品的第一侧突出,且纤维(F)的纤维区域(FB3)从模制品的第二侧突出。
以下细节和优选适用于本发明的由泡沫制成的模制品的两个实施方案。
本发明的模制品具有改进的机械特性。另外,在其中至少两个泡沫段已经彼此粘结的区域中,至少一根纤维(F)具有较好的固定。因此,其中至少两个泡沫段彼此粘合的区域用作纤维(F)的支撑部位。在本发明的优选实施方案中,当泡沫段通过粘合剂粘结和/或焊接而彼此粘结时,情况尤其如此。由于至少一根纤维(F)已较好的固定在泡沫中,所以其拔拉阻力增加。这也改进了模制品的再加工,例如在本发明的面板的制造中。此外,泡沫中的纤维取向可被更好地控制。
另一个优点被认为是,其中至少两个泡沫段彼此粘结的区域减少了模制品中任何可能的裂纹生长,因为它们阻止了裂纹的传播。这增加了本发明模制品的寿命和损伤容限。
本发明的模制品还有利地具有低的树脂吸附同时具有良好的界面粘结。当本发明的模制品被进一步加工以得到本发明的面板时,这种效果尤其重要。
与由一个泡沫段制成的相同尺寸的板坯相比,使用包含至少两个相互粘结的泡沫段的泡沫来制造本发明的模制品,允许对泡沫结构更好地控制。在相互粘合的泡沫段的情况下,可以实现例如更小、更均匀的泡孔尺寸、更各向异性的性质和更小的几何公差。
在模制品的一个优选实施方案中,因为泡沫段包含泡孔并且它们的各向异性达到至少50%、优选至少80%且更优选至少90%的程度,在一个实施方案中,泡沫的机械特性以及由此的模制品的机械特性也是各向异性的,这特别有利于本发明的模制品在风力涡轮机、运输领域、建筑领域、汽车制造、造船、铁路车辆结构、集装箱结构、卫生设施和/或航空航天中的使用,尤其是用于转子叶片。
泡沫段的粘合允许各向异性的泡沫段以受控的方式排列,从而实现例如具有承载能力或最小树脂吸附的机械特性的取向。
本发明的模制品因其各向异性而在至少一个方向上具有特别高的压缩强度。其另外具有高的闭孔含量和良好的真空稳定性。
根据本发明,通过本发明的模制品或由其得到的面板中的纤维增强泡沫,能够进一步改善粘结同时降低树脂吸附。根据本发明,纤维(单个地或优选以纤维束的形式)可首先以干燥形式和/或通过机械方法有利地引入到泡沫中。纤维或纤维束不是与相应的泡沫表面平齐地方式铺设,而是过量地铺设(因此能够改善粘结)或与本发明的面板中的相应外层直接连接。根据本发明,当施用到本发明的模制品上的外层是至少一个其他层(S1)以形成面板时,尤其如此。优选施用两个层(S1),其可为相同或不同的。更优选地,将两个相同的层(S1)、尤其是两个相同的纤维增强树脂层施用到本发明模制品的相对侧上,以形成本发明的面板。这种面板也称为“夹心材料”,在这种情况下,本发明的模制品也可称为“芯材料”。
因此,本发明的面板的显著特征是低的树脂吸附连同良好的剥离强度。鉴于各向异性泡沫段的合适取向,另外可以实现高抗皱性。此外,通过选择纤维类型及其比例和布置,可以以受控的方式建立高强度和刚度特性。低的树脂吸附的效果是重要的,因为在使用这种面板(夹心材料)的情况下,共同目标是结构特性应随最小重量增加。例如,在使用纤维增强外层的情况下,除了实际的外层和夹芯外,芯材料的树脂吸附也对总重量有贡献。然而,本发明的模制品或本发明的面板可降低树脂吸附,这可以减轻重量并节省成本。
本发明的模制品或面板的另一个优点被认为是,使用泡沫和相关产品使得相对更简单地在模制品的表面上并入一体化结构(integrated structure)例如槽或孔以及进一步处理模制品。在使用这种模制品(芯材料)的情况下,通常将这种结构例如引入到弯曲结构(深槽)中用于悬挂,用于通过液体树脂工艺(例如真空输注(孔))改善加工性,以及用于加速所述的处理操作(浅槽)。
通过使用泡沫段,还可以在粘结之前在早期阶段整合这种结构。因此,可在模制品中实现如果有的话也仅仅可通过高复杂程度的技术手段才能实现的几何结构。例如,可以在泡沫内并平行于泡沫表面将孔整合到模制品中。
其他改进/优点可得以实现,即将纤维以相对于泡沫的厚度方向(d)成0°至60°、更优选0°至45°的角度α引入到泡沫中。通常,以0°至<90°的角度α引入纤维在工业上是可进行的。
当纤维不仅以平行的方式被引入到泡沫中,而且其他纤维还以彼此成角度β(优选为>0至180°)的方式引入时,可以实现另外的改进/优点。另外,这实现了本发明的模制品的机械特性的改进。
同样有利的是当本发明面板中的(外部)树脂层通过液体注入方法或液体灌注方法——其中纤维可在加工过程中用树脂浸渍——施用时,并且机械特性得到改进。另外,由此可以节省成本。
以下进一步说明本发明。
根据本发明,模制品包含泡沫和至少一根纤维(F)。
泡沫包含至少两个相互粘结的泡沫段。这意味着泡沫可包含两个、三个、四个或更多个相互粘结的泡沫段。
泡沫段可基于本领域技术人员已知的任何聚合物。
例如,泡沫的泡沫段基于至少一种选自以下的聚合物: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;优选地,聚合物选自以下: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混合物;并且更优选地,聚合物为聚苯乙烯、聚苯乙烯和聚(2,6-二甲基苯醚)的混合物、苯乙烯-顺丁烯二酸酐聚合物和苯乙烯-丙烯腈聚合物的混合物,或苯乙烯-顺丁烯二酸酐聚合物(SMA)。
还适合作为泡沫的是热塑性弹性体。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),也称为聚(2,6-二甲基苯醚)。
由苯醚制备的合适的共聚物是本领域技术人员已知的。苯醚的合适的共聚物同样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-卤代的苯乙烯、环烷基化的苯乙烯、丙烯腈、丙烯酸酯、异丁烯酸酯、N-乙烯基化合物、顺丁烯二酸酐、丁二烯、二乙烯基苯和二丙烯酸丁二醇酯。
优选地,泡沫的所有泡沫段均基于相同的聚合物。这意味着泡沫的所有泡沫段均包含相同的聚合物,并且优选地,泡沫的所有泡沫段均由相同的聚合物组成。
泡沫的泡沫段例如由模制泡沫、挤出泡沫、反应性泡沫和/或母料泡沫制成,优选由挤出泡沫制成,尤其是以包括以下步骤的方法所制备的挤出泡沫:
I)在挤出机中提供聚合物熔体,
II)将至少一种发泡剂引入到步骤I)中提供的聚合物熔体中,以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通过至少一个模具孔(die aperture)从挤出机挤出到较低压力的区域中,并且使可发泡聚合物熔体膨胀,以获得膨胀泡沫,
IV)通过使膨胀泡沫通过成形工具而将来自步骤III)的膨胀泡沫定型,以获得挤出泡沫,
V)任选地将步骤IV)中获得的挤出泡沫进行材料去除处理,
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)期间施用至膨胀泡沫和/或在步骤IV)期间施用至膨胀泡沫,和/或
iv)任选地将至少一层(S2)在步骤IV)期间和/或直接在步骤IV)之后施用至挤出泡沫。
用于在步骤I)中在挤出机中提供聚合物熔体的合适的方法原则上是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化;同样也可将聚合物以熔融形式进料到挤出机中,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,因为用于制备聚合物熔体的聚合物的所需相应单体彼此反应以在挤出机中形成聚合物,由此提供聚合物熔体。
在本发明上下文中,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至450℃、优选为150至350℃且尤其优选为160至300℃。
在步骤II)中,将至少一种发泡剂引入到步骤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。
合适的发泡剂选自例如二氧化碳;烷烃,如丙烷、异丁烯和戊烷;醇类,如甲醇、乙醇、1-丙醇、2-丙醇、1-丁醇、2-丁醇、2-甲基丙醇和叔丁醇;醚类,如二甲醚;酮类,如丙酮和甲基乙基酮;卤代烃类,如氢氟丙烯;水;氮以及这些的混合物。
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至少一种发泡剂的含量为1重量%至15重量%、优选为2重量%至10重量%且尤其优选3重量%至8重量%,在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至500巴、优选为50至400巴且尤其优选为60至300巴。
在步骤III)中,将步骤II)中获得的可发泡聚合物熔体通过至少一个模具孔从挤出机挤出到较低压力的区域中,并且使可发泡聚合物熔体膨胀以获得膨胀泡沫。
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具孔是本领域技术人员已知的所有模具孔。模具孔可具有任何所需的形状;例如,其可为矩形、圆形、椭圆形、正方形或六边形。优选矩形的槽模和圆形的圆模。
在一个实施方案中,将可发泡聚合物熔体通过恰好一个模具孔、优选通过槽模挤出。在另一个实施方案中,将可发泡聚合物熔体通过多个模具孔、优选圆形或六边形模孔挤出,以获得大量的线料(strand),所述大量的线料在从模具孔挤出之后立即合并以形成膨胀泡沫。所述大量的股线也可仅在步骤IV)中通过成形模具合并。
优选地,加热至少一个模具孔。尤其优选地,当聚合物是无定形聚合物时,将模具孔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),并且当聚合物是半结晶聚合物时,将模具孔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,模具孔的温度为80至400℃、优选为100至350℃且尤其优选为110至300℃。
在步骤III)中,将可发泡聚合物熔体挤出到较低压力的区域中。所述较低压力的区域中的压力通常为0.05至5巴、优选为0.5至1.5巴。
在步骤III)中,将可发泡聚合物熔体挤出模具孔的压力通常为20至600巴、优选为40至300巴且尤其优选为50至250巴。
在步骤IV)中,通过使膨胀泡沫通过成形工具而将来自步骤III)的膨胀泡沫定型,以获得挤出泡沫。
膨胀泡沫的定型确定了步骤IV)中获得的挤出泡沫的外形。定型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具孔处。同样可能的是,成形工具设置在离模具孔一定距离处。
用于使膨胀泡沫定型的工具本身是本领域技术人员已知的。合适的成形工具包括例如片材定型器、滚筒输出器(roller takeoff)、心轴定型器、链式输出器和带式输出器。为了降低成形工具和挤出泡沫之间的摩擦系数,可以对工具进行涂覆和/或加热。
因此,步骤IV)中的定型使本发明的挤出泡沫的横截面的几何形状在至少一个维度上固定。优选地,挤出泡沫具有实际上正交的横截面。如果定型仅部分在特定方向进行,则挤出泡沫可以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具孔确定,其次由成形工具确定;这同样适用于挤出泡沫的宽度。
在步骤V)中,用于将步骤IV)中获得的挤出泡沫进行材料去除处理的合适的方法原则上是本领域技术人员已知的所有方法。例如,挤出泡沫可以通过锯切、铣削、钻孔或刨削进行材料去除处理。当挤出泡沫是热塑性泡沫时,热成型也是可能的,通过这种方法可避免材料去除处理中的切割损失和对纤维(F)的损坏。
对于本领域技术人员显而易见的是,所获得的挤出泡沫可用作本发明模制品中的泡沫段。例如,挤出泡沫也可首先被切割或锯切成较小的段,并且这些较小的段随后可被用作本发明模制中的泡沫段。此外,在接合之前,可将诸如槽、孔和凹槽的几何形状引入到挤出沫中,这些对模制品的性能或面板的制造或性能具有积极的影响。或者,泡沫当然也可在挤出之后直接使用。
基于正交坐标系,泡沫的长度称为x方向,宽度称为y方向,且厚度称为z方向。当挤出泡沫通过挤出来制造时,x方向对应于挤出泡沫的挤出方向。
合适的添加剂原则上是本领域技术人员已知的所有添加剂,例如成核剂、阻燃剂、染料、工艺稳定剂、加工助剂、光稳定剂和颜料。
对于在一个实施方案中施用于挤出泡沫的层(S2),下文进一步描述的细节和优选是适用的。
根据本发明,泡沫的至少两个泡沫段彼此粘结。可通过本领域技术人员已知的任何方法将所述至少两个泡沫段粘结。至少两个泡沫片段的粘结在专业技术人员中也被称为接合。
以下选项中的至少一个优选地适用于本发明的模制品:
i)至少两个相互粘结的泡沫段已通过粘合剂粘结和/或焊接而彼此粘结,并且优选地,模制品的泡沫的所有相互粘结的泡沫段已通过热焊接和/或粘合剂粘结而彼此粘结,和/或
ii)单个泡沫段的长度(x方向)为至少2mm、优选20至8000mm、更优选100至400mm,宽度(y方向)为至少2mm、优选5至4000mm、更优选25至2500mm,且厚度(z方向)为至少2mm、优选至少5mm、更优选至少25mm、最优选30至80mm,和/或
iii)单个泡沫段具有板坯形状,和/或
iv)单个泡沫段的长度(x方向)与厚度(z方向)之比为至少5、优选至少10、更优选至少20、最优选20至500,和/或
v)单个泡沫段的宽度(y方向)与厚度(z方向)之比为至少3、优选至少5、更优选至少10、最优选10至250,和/或
vi)至少一根纤维(F)穿过泡沫的两个相互粘结的泡沫段之间的至少一个粘结表面,并且优选地,所有纤维(F)的至少20%穿过泡沫的两个相互粘结的泡沫段之间的至少一个粘结表面,更优选所有纤维(F)的至少50%,和/或
vii)至少一根纤维(F)以≥20°、优选≥35°、尤其是40°至90°的角度δ部分地或完全地穿过两个相互粘结的泡沫段之间的至少一个粘结表面,和/或
viii)至少两个相互粘结的泡沫段之间的至少一个粘结表面、优选所有粘结表面的厚度为至少2μm、优选至少5μm、更优选20至2000μm、最优选50至800μm,和/或
ix)至少两个相互粘结的泡沫段之间的至少一个粘结表面、优选所有粘结表面的厚度大于相互粘结的泡沫段的平均泡孔壁厚的总和,优选比泡孔壁厚总和大2至1000倍且优选大5至500倍。
粘结表面的厚度应理解为意指泡沫段——其中泡沫段的孔隙率为<10%——之间的区域的厚度。孔隙率被理解为意指空腔体积(孔体积)与泡沫的总体积之比(无量纲)。例如通过显微镜图像的图像分析来确定。然后将由此确定的空腔体积除以泡沫的总体积。
可将至少两个相互粘结的泡沫段彼此粘结,以获得多层泡沫。在本发明的上下文中,“多层”应理解为意指至少二层泡沫。同样泡沫可为例如三层、四层或五层。对本领域技术人员而言显而易见的是,通过将两个泡沫段组合而获得两层泡沫,通过将三个泡沫段组合而获得三层泡沫,等等。显而易见的是,所述至少二层泡沫将比单个泡沫段具有更大的厚度。
这种多层泡沫优选通过板坯形式的至少两个泡沫段的粘结来获得。
所述多层泡沫也可被切割成更小的单元,例如,其又可以彼此粘结。
例如,多层泡沫可以直角切割成板坯,并且由此获得的较小部分可以彼此粘结。
所述至少两个相互粘结的泡沫段可通过本领域技术人员已知的任何方法彼此粘结,并且优选地,所述至少两个彼此粘结的泡沫段通过粘合剂粘结和/或焊接而彼此粘结。
粘合剂粘结和焊接本身是本领域技术人员已知的。
粘合剂粘结包括将至少两个彼此粘结的泡沫段通过合适的粘合剂(粘合促进剂)而粘结。
合适的粘合剂是本领域技术人员已知的。例如,可以使用单组分或双组分粘合剂、热熔粘合剂或分散粘合剂。合适的粘合剂基于例如聚氯丁二烯、聚丙烯酸酯、苯乙烯-丙烯酸酯共聚物、聚氨酯、环氧化物或三聚氰胺-甲醛缩合产物。粘合剂可例如通过喷涂、涂抹、滚压、浸渍或润湿施用到泡沫段上。粘合剂粘结的一般性综述见于“Habenicht,Kleben–Grundlagen,Technologien,Anwendung[Adhesive Bonding–Basics,Technology,Application]",Springer(2008)”。
焊接方法同样是本领域技术人员已知的。
相互粘结的泡沫段可例如通过热焊接、热铆接、加热元件焊接、高频焊接、圆形焊接、旋转摩擦焊接、超声波焊接、振动焊接、热气体焊接或溶剂焊接而彼此粘结。
相互粘结的泡沫段可彼此直接焊接,或者还可以使用其他层,尤其是低熔点聚合物薄膜。这些能够实现较低的焊接温度、较低的压缩和因此泡沫段的低压缩。所用的层也可为其他材料,例如由有机、无机、金属或陶瓷纤维制成的纤维网、织物或稀松布形式的纤维材料,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。
用于此目的的方法是本领域技术人员已知的,并且记载于例如EP 1213119、DE4421016、US 2011/082227、EP1318164和EP 2578381中。
热焊接的方法本身是本领域技术人员已知的。这包括将相应的表面暴露于热源。相应的热源或设备是本领域技术人员已知的。优选使用选自加热刀片、加热格栅和加热板的设备进行热焊接。热焊接可连续进行,例如使用加热片;同样可使用加热板或加热格栅进行镜面焊接。同样可能的是,部分或全部进行热焊接,即用电磁辐射供热。
在至少两个泡沫段的粘结中,在至少两个泡沫段的表面之间形成至少一个粘结表面。如果两个泡沫段通过热焊接彼此粘结,则该粘结表面在专业技术人员中也称为焊接缝、焊缝或焊接区。
粘结表面可具有任何所需的厚度,并且通常厚度为至少2μm、优选至少5μm、更优选20至2000μm且最优选50至800μm。
泡沫段通常包含泡孔。泡沫段的平均泡孔壁厚可通过本领域技术人员已知的任何方法来确定,例如通过光或电子显微镜通过统计评估泡孔壁厚。
优选地,根据本发明,至少两个相互粘结的泡沫段之间的结合表面大于两个泡沫段的平均泡孔壁厚的总和。
还优选本发明的模制品,其中泡沫段包含泡孔,其中
i)至少两个泡沫段、优选所有泡沫段的至少50%、优选至少80%且更优选至少90%的泡孔是各向异性的,和/或
ii)至少两个泡沫段、优选所有泡沫段的至少50%、优选至少80%且更优选至少90%的泡孔的最大尺寸(a方向)与最小尺寸(c方向)之比为≥1.05、优选为1.1至10、尤其优选为1.2至5,和/或
iii)基于其最大尺寸(a方向),至少两个泡沫段、优选所有泡沫段的至少50%、优选至少80%且更优选至少90%的泡孔以相对于模制品的厚度方向(d)成≤45°、优选≤30°且更优选≤5°的角度γ排列。
各向异性泡孔在不同的空间方向具有不同的尺寸。泡孔的最大尺寸称为“a”方向,且最小尺寸称为“c”方向。第三个尺寸称为“b”方向。
泡孔的尺寸可例如通过光学显微照片或电子显微照片确定。
还优选的是,至少两个泡沫段、优选所有泡沫段的至少50%、优选至少80%且更优选至少90%的泡孔的最小尺寸(c方向)的平均尺寸为0.01至1mm、优选为0.02至0.5mm且尤其为0.02至0.3mm。
至少两个泡沫段、优选所有泡沫段的至少50%、优选至少80%且更优选至少90%的泡孔的最大尺寸(a方向)的平均尺寸通常为不大于20mm、优选为0.01至5mm、尤其为0.03至1mm且更优选为0.03至0.5mm。
进一步优选的是,至少两个泡沫段、优选所有泡沫段的至少50%、优选至少80%且更优选至少90%的泡孔是正交各向异性或横向各向同性的。
正交各向异性的泡孔应理解为意指各向异性泡孔的一种特殊情况。正交各向异性意指泡孔具有三个对称平面。在对称平面彼此正交取向——基于正交坐标系——的情况下,泡孔的尺寸在所有三个空间方向上,即在a方向、b方向和c方向上都是不同的。
横向各向同性意指泡孔具有三个对称平面。然而,泡孔相对于围绕两个对称平面的交叉轴线的旋转是不变的。在对称平面彼此正交取向的情况下,泡孔仅在一个空间方向上的尺寸不同于泡孔在另两个方向上的的尺寸。例如,泡孔在a方向上的尺寸不同于在b方向上和在c方向上的尺寸,并且b方向上的尺寸与在c方向上的尺寸相同。
还优选的是,至少两个泡沫段、优选所有泡沫段的闭孔含量为至少80%、优选为至少95%、更优选为至少98%。根据DIN ISO 4590(按照2003年8月的德国版)确定泡沫段的闭孔含量。闭孔含量描述了总体积中闭孔体积的比例。
进一步优选的是,在模具中,纤维(F)以相对于至少两个泡沫段、优选所有泡沫段的至少50%、优选至少80%且更优选至少90%的泡孔的最大尺寸(a方向)成≤60°,优选≤50°的角度ε。
优选地,至少两个泡沫段、优选所有泡沫段的泡孔的各向异性特性是由在本发明的一个实施方案中优选的挤出方法产生的。由于在步骤III)中将可发泡聚合物熔体挤出并在步骤IV)将由此获得的膨胀泡沫中定型,由此制造的挤出泡沫通常获得了由各向异性泡孔产生的各向异性特性。
如果泡沫段的特性是各向异性的,则这意味着泡沫段的特性在不同的空间方向上是不同的。例如,泡沫段在厚度(z方向)上的压缩强度可能不同于在长度(x方向)和/或宽度(y方向)上的压缩强度。
进一步优选本发明的模制品,其中
i)泡沫的至少两个泡沫段、优选所有泡沫段的至少一个机械特性、优选所有机械特性是各向异性的、优选是正交各向异性的或横向各向同性的,和/或
ii)挤出泡沫的至少一个弹性模量、优选所有弹性模量以各向异性的、优选正交各向异性的或横向各向同性的材料的方式表现,和/或
iii)泡沫的至少两个泡沫段、优选所有泡沫段在厚度(z方向)上的压缩强度与泡沫的至少两个泡沫段、优选所有泡沫段在长度(x方向)上的压缩强度之比和/或泡沫的至少两个泡沫段、优选所有泡沫段在厚度(z方向)上的压缩强度与泡沫的至少两个泡沫段、优选所有泡沫段在宽度(y方向)上的压缩强度之比为≥1.1、优选为≥1.5、尤其优选为2至10。
机械特性应理解为意指本领域技术人员已知的泡沫的所有机械特性,例如强度、刚度或弹性、延展性和韧性。
弹性模量本身是本领域技术人员已知的。弹性模量包括例如弹性的模量、压缩模量、扭转模量和剪切模量。
关于机械特性或弹性模量的“正交各向异性”意指材料具有三个对称平面。在对称平面彼此正交取向的情况下,可以使用正交坐标系。因此,泡沫段的机械特性或弹性模量所有三个空间方向(x方向、y方向和z方向)上是不同的。
关于机械特性或弹性模量的“横向各向同性”意指材料具有三个对称平面,并且模量相对于围绕两个对称平面的交叉轴线的旋转是不变的。在对称平面彼此正交取向的情况下,泡沫段的机械特性或弹性模量在一个空间方向上不同于在另外两个空间方向上的,但在另外两个空间方向上是相同的。例如,在z方向上的机械特性或弹性模量不同于x方向和y方向上的机械特性或弹性模量;而在x方向和y方向上是相同的。
对于本领域技术人员而言清楚的是,根据泡沫段彼此粘结的方式,泡沫以及由此得到的本发明的模制品也可为各向异性或各向同性的。优选地,相互结合的泡沫段以及泡沫均是各向异性的。
泡沫的泡沫段的压缩强度根据DIN EN ISO 844(2009年10月版)来确定。
泡沫段在厚度(z方向)上的压缩强度通常为0.05至5MPa、优选为0.1至2MPa、更优选为0.1至1MPa。
泡沫段在长度(x方向)上和/或在宽度(y方向)上的压缩强度通常为0.05至5MPa、优选为0.1至2MPa、更优选为0.1至1MPa。
存在于模制品中的纤维(F)是单纤维或纤维束,优选纤维束。合适的纤维(F)是本领域技术人员已知的可形成纤维的所有材料。例如,纤维(F)是有机、无机、金属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。所述纤维束由若干单纤维(长丝)组成。每束的单纤维的数量在玻璃纤维的情况下为至少10根、优选为100至100 000根、更优选为300至10000根且在碳纤维的情况下更优选为1000至50 000根,并且在玻璃纤维的情况下尤其优选为500至5000根且在碳纤维的情况下尤其优选为2000至20 000根。
根据本发明,至少一根纤维(F)在模制品内存在有纤维区域(FB2)并被泡沫包围,同时纤维(F)的纤维区域(FB1)从模制品的第一侧突出,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)的总长度的任意所需比例。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)总长度的1%至45%、优选2%至40%且更优选5%至30%,且纤维区域(FB2)占纤维(F)总长度的10%至98%、优选20%至96%且更优选40%至90%。
在另一个优选的实施方案中,纤维(F)的纤维区域(FB1)从中突出的模制品的第一侧与纤维(F)的纤维区域(FB3)从中突出的模制品的第二侧相对。
优选地,纤维(F)以相对于模制品的厚度方向(d)成角度α或相对于模制品的第一侧的正交(的表面)成直角引入到模制品中。角度α可以采取0°至90°的任意值。例如,纤维(F)以相对于模制品的厚度方向(d)成0°至60°、优选0°至50°、更优选0°至15°或10°至70°、尤其30°至60°、更优选30°至50°、甚至更优选30°至45°且尤其45°的角度α引入到泡沫中。
在另一个实施方案中,至少两根纤维(F)以两个不同的角度α(α1和α2)引入,其中角度α1优选为0°至15°且第二角度α2优选为30°至50°;尤其优选地,α1为0°至5°且α2为40°至50°。优选地,本发明模制品中的所有纤维(F)具有相同的角度α或至少近似相同的角度(差别不大于+/-5°、优选+/-2°,更优选+/-1°)。
优选地,本发明的模制品包含多根纤维(F),优选为纤维束,和/或包含大于10根纤维(F)或纤维束/m2、优选大于1000根/m2,更优选4000至40 000根/m2。
所有纤维(F)可以彼此平行地方式存在于模制品中。根据本发明,同样可能和优选的是,两根或多根纤维(F)以彼此成角度β存在于模制中。在本发明的上下文中,角度β理解为意指第一纤维(F1)在模制品的第一侧的表面上的正交投影与第二纤维(F2)在模制品的表面上的正交投影之间的角度,两根纤维均已被引入到模制品中。
角度β优选为β=360°/n,其中n为整数。优选地,n为2至6、更优选为2至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°至100°、110°至130°或在170°至190°。在另一个实施方案中,多于两根纤维(F)以彼此成角度β引入,例如三根或四根纤维(F)。这些三根或四根纤维(F)对于两根相邻的纤维可分别具有两个不同的角度β(β1和β2)。优选地,所有的纤维(F)对于两根相邻的纤维(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°,且第四纤维(F4)与第一纤维(F1)之间的角度β4同样为90°。然后,以顺时针方向,第一纤维(F1)(参照)与第二光纤(F2)、第三光纤(F3)和第四光纤(F4)之间的角度β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,且与第一纤维(F1)成角度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。在本发明上下文中“相似”应理解为意指,相对于其他方向的每个方向上的纤维数量之间的差<30%、更优选<10%且尤其优选<2%。
纤维或纤维束可以不规则或规则形式引入。优选以规则形式引入纤维或纤维束。在本发明的上下文中,“规则形式”应理解为意指所有纤维彼此平行排列,并且至少一根纤维或纤维束与所有直接相邻的纤维或纤维束具有相同的距离(a)。尤其优选地,所有纤维或纤维束与所有直接相邻的纤维或纤维束均具有相同的距离。
在另一个优选的实施方案中,引入纤维或纤维束,使得基于正交坐标系(其中厚度方向(d)对应于z方向)它们各自在x方向具有彼此相同的距离(ax)且在y方向具有相同的距离(ay)。尤其优选地,它们在x方向和y方向上均具有相同的距离(a),其中a=ax=ay。
如果两根或更多根纤维(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)的规则形式,并且彼此平行且与第一纤维(F1)成角度β的第二纤维(F2)优选具有第二距离(a2)的规则形式。在一个优选的实施方案中,第一纤维(F1)和第二纤维(F2)分别具有距离(a)的规则形式。在这种情况下,a=a1=a2。
如果纤维或纤维束以彼此成角度β引入到泡沫中,则优选纤维或纤维束在各个方向上遵循规则形式。
图1以透视图示出了由泡沫(1)制成的本发明的模制品的一个优选实施方案的示意图。(2)表示模制品的第一侧(的表面),且(3)表示相应模制品的第二侧。从图1还可以看出,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(4a)的一端和由此的纤维区域(FB1)从模制品的第一侧(2)突出,同时构成纤维区域(FB3)的纤维的另一端(4b)从模制品的第二侧(3)突出。中间的纤维区域(FB2)在模制品内,并因此被泡沫包围。
在图1中,纤维(4)(其例如为单纤维或纤维束,优选纤维束)以相对于模制品的厚度方向(d)成角度α或者相对于模制品的第一侧(2)(的表面)成直角。角度α可以为0°至90°的任意值,且通常为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°、尤其为30°至50°、甚至更优选为30°至45°、尤其为45°。为了清楚起见,图1仅示出了单纤维(F)。
图3以示例的方式示出了一些不同角度的示意图。图3所示的由泡沫(1)制成的模制品包含第一纤维(41)和第二纤维(42)。在图3中,为了更清楚,仅示出了两根纤维(41)和(42)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)的表面的正交直线(O)形成了第一角度α(α1)。第二纤维(42)相对于第一侧(2)的表面的正交直线(O)形成了第二角度α(α2)。第一纤维(41)在模制品(41p)的第一侧(2)上的正交投影与第二纤维(42)在模制品(42p)的第一侧(2)上的正交投影形成了角度β。
图4以示例的方式示出了纤维(4)与两个相互粘结的泡沫段(9,10)之间的粘结表面之间的角度δ的示意图。图4所示的由泡沫(1)制成的模制品包含纤维(4)、第一泡沫段(9)、第二泡沫段(10)和结合表面(8)。为了清楚起见,图4仅示出了一根纤维(4)、仅两个泡沫段(9,10)和仅一个粘合表面(8)。显而易见的是,模制品可包含多于一个粘结表面(8)、多于两个的泡沫段(9,10)和多于一根纤维(4)。纤维(4)已经以相对于粘结表面(8)成≥20°、优选≥35°、尤其优选40°至90°的角度δ引入到泡沫中。
本发明还提供包含本发明的至少一个模制品和至少一个层(S1)的面板。在某些情况下,“面板”也可被称为“夹心结构”、“夹心材料”、“层压材料”和/或“复合材料制品”。
在面板的一个优选实施方案中,面板具有两层(S1),并且两层(S1)分别安装在模制品的的一侧——与模制品的相应另一侧相对——上。
在本发明的面板的一个实施方案中,层(S1)包含至少一种树脂,该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,并且该树脂尤其为胺固化的环氧树脂、潜在固化的环氧树脂、酸酐固化的环氧树脂或由异氰酸酯和多元醇形成的聚氨酯。此类树脂体系是本领域技术人员已知的,例如已知于Penczek等人(Advances in Polymer Science,184,第1-95页,2005)、Pham等人(Ullmann's Encyclopedia of Industrial Chemistry,第13卷,2012)、Fahnler(Polyamide,Kunststoff Handbuch 3/4,1998)和Younes(WO12134878 A2)。
根据本发明还优选面板,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)在模制品的至少一侧与至少一层(S1)之间,面板具有至少一层(S2),所述层(S2)优选由二维纤维材料或聚合物薄膜组成,更优选由纤维网、稀松布或织物形式的玻璃纤维或碳纤维组成。
在本发明面板的另一个实施方案中,所述至少一层(S1)另外包含至少一种纤维材料,其中
i)纤维材料包含一层或多层短切纤维、纤维网、稀松布、编织物和/或织物形式的纤维,优选为稀松布或织物形式,更优选为具有每个稀松布或织物的基重为150至2500g/m2的稀松布或织物形式,和/或
ii)纤维材料包含有机、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个优选实施方案。示出了本发明的面板(7)的二维侧视图,其包含如上所详述的本发明的模制品(1),例如在图1的实施方案的上下文中。除非另有说明,否则附图标记在图1和图2中的其他缩写的情况下具有相同的含义。
在根据图2的实施方案中,本发明的面板包含由(5)和(6)表示的两层(S1)。因此两层(5)和(6)分别位于模制品(1)相对的两侧上。两层(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/或在模制品(1)与第二层(6)之间可以存在一个或多个其他层。如上面对于图1所述,为了简单起见,图2还示出了具有(4)的单纤维(F)。关于纤维或纤维束的数量,在实践中,类似的说明适用于以上对图1所述的那些。
本发明还提供一种制造本发明的模制品的方法,其中将至少一根纤维(F)部分地引入到泡沫中,其结果是纤维(F)在模制品内存在有纤维区域(FB2)并被泡沫包围,同时纤维(F)的纤维区域(FB1)从模制品的第一侧突出,且纤维(F)的纤维区域(FB3)从模制品的第二侧突出。
原则上,引入纤维(F)和/或纤维束的合适的方法是本领域技术人员已知的那些方法。合适的方法记载于,例如WO 2006/125561或WO 2011/012587中。
在本发明方法的一个实施方案中,通过将至少一种纤维(F)使用针将其缝合而部分地引入到泡沫中,优选通过步骤a)至f)进行所述的部分引入:
a)任选地将至少一层(S2)施用到泡沫的至少一侧上,
b)对于每根纤维(F)在泡沫和任意层(S2)中产生一个孔,该孔从泡沫的第一侧延伸到第二侧并穿过任意层(S2),
c)在泡沫的第二侧上提供至少一根纤维(F),
d)使针从泡沫的第一侧穿过孔到泡沫的第二侧,并使针穿过任意层(S2),
e)在泡沫的第二侧上,将至少一根纤维(F)固定在针上,以及
f)将针与纤维(F)一起通过孔返回,使得纤维(F)在模制品内存在有纤维区域(FB2)并被泡沫包围,同时纤维(F)的纤维区域(FB1)从模制品的第一侧或从任意层(S2)突出,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)。
以下对本发明方法的步骤a)至f)的细节和优选相应地适用于将纤维(F)引入到本发明的模制品的方法的步骤a)至f)。
步骤a)中的至少一层(S2)的施用可以例如如上所述在步骤IV)期间和/或直接在步骤IV)之后进行。
在一个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,通过使针从泡沫的第一侧穿过到泡沫的第二侧来产生从泡沫的第一侧到第二侧的孔。
在该实施方案中,至少一根纤维(F)的引入可包括例如以下步骤:
a)任选地将至少一层(S2)施用到泡沫的至少一侧上,
b)在泡沫的第二侧上提供至少一根纤维(F),
c)对于每根纤维(F)在泡沫和任意层(S2)中产生一个孔,该孔从泡沫的第一侧延伸到第二侧并穿过任意层(S2),并且通过使针穿过泡沫并穿过任意层(S2)来产生孔,
d)在泡沫的第二侧上,将至少一根纤维(F)固定在针上,
e)将针与纤维(F)一起通过孔返回,使得纤维(F)在模制品内存在有纤维区域(FB2)并被泡沫包围,同时纤维(F)的纤维区域(FB1)从模制品的第一侧或从任意层(S2)突出,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),以及
g)任选地切开在针上形成的纤维(F)的环。
在一个优选的实施方案中,所使用的针是钩针,并且在步骤d)中将至少一根纤维(F)钩在钩针中。
在另一个优选实施方案中,根据上述步骤,将多根纤维(F)同时引入到泡沫中。
本发明还提供一种用于制造本发明面板的方法,其中将至少一层呈反应性粘性树脂形式的层(S1)施用于本发明的模制品上并通过以下方法固化: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,尤其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。液体浸渍方法本身是本领域技术人员已知的,并且详细记载于例如WileyEncyclopedia of Composites(第2版,Wiley,2012),Parnas等人(Liquid CompositeMoulding,Hanser,2000)以及Williams等人(Composites Part A,27,第517-524页,1997)。
可使用各种辅助材料来制造本发明的面板。用于通过真空灌注来制造的合适的辅助材料为,例如,真空膜,优选由尼龙制成;真空密封带;流动助剂,优选由尼龙制成;分离膜,优选由聚烯烃制成;分离织物(tearoff fabric),优选由聚酯制成;及半透膜,优选隔膜薄膜,更优选PTFE薄膜;吸收性羊毛状物(absorption fleece),优选由聚酯制成。合适的辅助材料的选择由待制造的部件、所选择的方法和所使用的材料(尤其是树脂体系)来决定。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流动助剂、由聚烯烃制成的分离膜、由聚酯制成的分离织物,以及以PTFE薄膜形式的半透膜,以及由聚酯制成的吸收性羊毛状物。
在本发明面板的制造方法中,这些辅助材料可以以各种方式使用。更优选地,通过借助于真空灌注施用纤维增强的外层来由模制品制造面板。在典型的结构中,为了制造本发明的面板,将纤维材料和任选的其他层施用到模制品的上侧和下侧。随后,放置分离织物和分离膜。在液体树脂体系的灌注中,可使用流动助剂和/或隔膜薄膜。特别优选以下变形:
i)仅在结构的一侧上使用流动助剂,和/或
ii)在结构的两侧上均使用流动助剂,和/或
iii)具有半透膜的结构(VAP结构);优选将半透膜覆盖在模制品的整个区域上,在模制品的一侧或两侧上使用流动助剂、分离膜和分离织物,并且借助真空密封带将相对于模具表面的半透膜密封,并且将吸收性羊毛状物插在远离模制品的半透膜的一侧上,结果是将空气在整个区域上向上排空,和/或
iv)使用由隔膜薄膜制成的真空袋,其优选放置与模制品的开口侧(gate side)相对的位置处,借助真空袋将空气从与该开口相对一侧排空。
随后,使该结构配备有用于树脂体系的开口和用于排空的开口。最后,在整个结构上施用真空膜并用密封带密封,并且将整个结构排空。在灌注树脂体系之后,在保持真空的条件下进行树脂体系的反应。
本发明还提供本发明的模制品或本发明的面板用于风力涡轮机中的转子叶片、在运输领域、建筑领域、汽车制造、造船、铁路车辆结构、容器结构、卫生设施和/或航空航天中的用途。
本发明通过以下实施例进行说明。
实施例
实施例I1、C2、I3、C4、C8和C9
首先,用不同的成分制造板坯形式的泡沫段。在串联挤出系统中,泡沫段作为包含聚苯醚(PPE)和聚苯乙烯(PS)的挤出泡沫来制造。熔融挤出机(ZSK 120)连续供应聚苯醚母料(PPE/PS母料,Noryl C6850,Sabic)和聚苯乙烯(PS 148H,BASF),以制造包含25份PPE和75份PS的整个共混物。另外,通过吸入将添加剂例如滑石(0.2份)计量加入PS母料(PS148H,BASF)中。将发泡剂(二氧化碳、乙醇和异丁烷)以各种组成在压力下注入到注入口中。包括发泡剂和添加剂在内的总通过量为750kg/h。将可发泡聚合物熔体在下游冷却挤出机(ZE 400)中冷却并通过狭槽模头挤出。将膨胀泡沫体通过加热的定型器(其表面涂覆有聚四氟乙烯)经输送带移除,并形成板坯。机械加工前的典型板坯尺寸的宽度为约800mm且厚度为60mm。挤出泡沫的平均密度为50kg/m3。
在示例I1中,通过焊接两个泡沫板坯来产生粘结表面。在这种情况下,首先借助研磨机去除表面并使其平整。随后,将这些泡沫板坯与加热元件焊接机无接触地加热并接合。平均焊接温度为350℃,加热时间为2.5-4.0s,且加热元件与泡沫板坯之间的距离为0.7mm。所造成的焊接厚度损失为3-5mm。随后将由此获得的泡沫刨平成厚度为20mm。
所用的比较是未焊接的板坯,其被刨平至厚度为20mm(比较实施例C2)。
所用的另一个比较是根据比较实施例C2的板坯,另外已经通过簇绒法将纤维引入到该板坯中(比较实施例C8)。
同样被用作比较的是根据实施例I1的焊接板坯,其中已经通过簇绒法引入了纤维(比较实施例C9)。
在簇绒方法中,使用了来自Schmitz的针系统名称为0647LH0545D300WE240RBNSPGELF与CANU 83:54S 2NM 250的簇绒针。这是购自Schmitz的最小的簇绒针,其未经过特别制造。
在簇绒法中,用簇绒针使纤维束从泡沫的第一侧直接穿过泡沫到泡沫的第二侧,然后将簇绒针拉回到第一侧。在泡沫的第二侧上形成了纤维束的环。由于在簇绒法中,在使簇绒针与纤维束一起穿过时在泡沫中产生孔,所以作用于簇绒针和纤维束的摩擦力较高;同时,针眼中的纤维束的弯曲半径非常小。这种组合导致了纤维束的切断和接合,使得它们不总是形成环,此外,没有将纤维束的所有纤维都引入到泡沫中。
为了非常显著地消除这些缺点并确保与本发明用于引入纤维的方法的可比性,比较实施例C8和C9中的簇绒法按照以下进行:
首先,用上述簇绒针预先制作孔,然后如上所述将纤维束与簇绒针一起引入到泡沫中。
使用与实施例I1和I3以及比较实施例C2和C4中相同的纤维束(粗纱)。
将聚酯泡沫在挤出系统中通过多孔模具进行泡沫挤出;在该过程中将单个线料直接粘结。将聚合物(80份PET(瓶级,粘度指数0.74,M&G,P76)和20份在该过程中再循环的材料的混合物)、成核剂(滑石,0.4份,母料于PET)、扩链剂(PMDA,0.4份,母料于PET)和聚烯烃弹性体(Proflex CR0165-02,10份,母料于PET)的混合物在同向旋转双螺杆挤出机(螺杆直径为132mm)中熔融并混合。熔融后,加入环戊烷作为发泡剂(环戊烷,4.5份)。在加入发泡剂之后,将均匀熔体直接通过下游壳体和静态混合器冷却。挤出机壳体的温度为300℃至220℃。在其到达多孔模具之前,熔体必须穿过熔体过滤器。多孔模具具有8排,每排具有多个独立的孔。总通过量为约150kg/h。模具压力保持在至少50巴。可发泡聚合物熔体通过多孔模具发泡,并且单个线料通过定型器单元合并成块状。随后,将挤出的板坯通过材料去除至具有板坯厚度为35mm的恒定的外部几何形状来进行修整,并通过平行于挤出方向的热焊接来接合。泡沫的平均密度为50kg/m3。
在实施例I3中,通过将泡沫板坯借助平行于挤出方向的热焊接坯而接合来产生内部支撑部位。所选择的方法是在借助聚四氟乙烯涂覆的加热板加热泡沫板坯之后进行接触焊接。随后,将由此获得的泡沫刨平至厚度为20mm。
所用的比较实施例是没有焊接的泡沫板坯,其被刨平至厚度为20mm(比较实施例C4)。
通过扫描电子显微照片的统计评估来确定泡沫段的平均泡孔壁厚和粘结表面的厚度。以类似的方式确定支撑部位的平均壁厚。表1中示出了典型的尺寸。
处理模制品的一个重要因素是,在处理过程中纤维在泡沫板坯内保持固定。所确定的定量量度是通过拉拔测试的拔拉阻力或拉出纤维所需的力。
在实施例I1和I3以及比较例C2和C4中,首先将粗纱形式的纤维(E玻璃,400tex)垂直于表面并垂直于粘结表面手工引入到泡沫中。为此,通过组合缝合/钩挂方法引入纤维粗纱。首先,使用钩针(直径约0.80mm)将泡沫的第一侧至第二侧完全穿透。在第二侧上,将粗纱钩在钩针的钩中,然后通过针从第二侧拉回到泡沫的第一侧。最后,将第二侧上的粗纱切断,并且所形成的粗纱环悬挂在针上。
在引入粗纱之后,在所有的实施例和比较实施例中,借助小螺栓将粗纱环固定到测力传感器上,在测力传感器已平衡到零之后,将泡沫以50mm/min的速度移动。使用具有有效分辨率为1mN的1kN测力传感器。在机器移动过程中手工固定泡沫。为了评估拉出力,评估力最大值(三次测量的平均值)。在该测试中,最大力始终出现在测试开始时,因为初始粘结摩擦力大于随后的滑动摩擦力。
在通过本发明的方法将纤维粗纱整合到支撑部位的情况下的最大拉出力明显比在固定到平直泡沫中的情况下的最大拉出力要高(I1和I3相对于C2和C4)。
相比之下,支撑部位对借助簇绒法(比较实施例C9)引入纤维粗纱的拉出力没有明显的影响。这表明,支撑部位在簇绒法中被严重损坏和/或者夹紧力被孔的尺寸降低。
表1
实施例I5:
由上述PPE/PS泡沫(实施例I1)制造包含相互粘结的泡沫段并包封纤维的模制品。在挤出泡沫的情况下,接合的泡沫板坯以其具有厚度为20mm的现有形式使用。粘结表面恰好通过接合板坯的中间。板坯尺寸为800mm×600mm;两个接合的板坯元件的平均厚度最初为60mm;在材料去除减少厚度之后,获得了用于最终粘结的厚度为10mm的泡沫段。
两个泡沫段在厚度方向(d)上的压缩强度为0.8MPa,因此比在纵向或横向上的高约3.9倍(根据DIN EN ISO 844)。另外,已通过显微镜图像分析的泡孔的最大尺寸(a方向)沿厚度方向(d)取向。将纤维以相对于厚度方向(d)为45°的角度α并因此同样与粘结表面成45°的角度引入。所用的纤维是玻璃粗纱(S2玻璃,406tex,AGY)。玻璃纤维以等距离a=12mm的规则矩形形式引入。这得到面积密度为27 778粗纱/m2,所有纤维都通过粘结表面固定。在两侧上,约5.5mm的玻璃纤维另外作为过量留在外层上,以便改进与随后作为外层引入的玻璃纤维垫的粘结。通过组合针/钩方法以自动方式引入纤维或纤维粗纱。首先,使用钩针(直径约0.80mm)将泡沫的第一侧到第二侧完全穿透。在第二侧,将粗纱钩在钩针的钩中,然后通过针从第二侧拉回到泡沫的第一侧。最后,将在第二侧上的粗纱切断,并且切开在针上形成的粗纱环。
利用泡沫中的支撑部位能够明显更好地固定纤维,从而更好地处理模制品。另外,可减少在模制品的材料去除处理中的纤维拉出。
实施例I6:
由上述PET泡沫(实施例I3)制造包含粘结泡沫段和包封纤维的模制品。在挤出泡沫的情况下,首先通过热焊接将几个长度为1500mm、宽度为700mm、厚度为35mm的泡沫板坯粘结。随后通过锯条垂直于粘结表面并垂直于初始的未接合板坯的纵向方向而将所获得的总厚度为700mm的泡沫切割成宽度/长度尺寸为700mm×700mm且厚度为20mm的板坯。因此,泡沫板坯由垂直于板坯厚度取向的约22个接合的泡沫段组成。泡沫元件的在接合板坯的厚度方向(d)上的压缩强度为0.6MPa,因此比在纵向或横向上的高约4.1倍(根据DIN EN ISO844)。
另外,通过显微镜图像分析的泡孔的最大尺寸(a方向)取向为厚度方向(d)。最大尺寸(a方向)的长度为约0.5mm;最小尺寸(c方向)为约0.2mm。将纤维以相对于厚度方向(d)成45°的角度α且因此同样与结合表面成45°的角度δ引入。类似于实施例I5引入纤维。已通过粘结表面固定了27 778粗纱/m2中的约30%。
利用泡沫中的支撑部位能够明显更好地固定纤维,从而更好地处理模制品。此外,可减少在模制品的材料去除处理中的纤维拉出。
由实施例I5的模制品制造面板。通过真空灌注产生纤维增强外层。除了所用的树脂体系、泡沫板坯和玻璃粗纱之外,还使用以下辅助材料:尼龙真空膜、真空密封带、尼龙流动助剂、聚烯烃分离膜、聚酯分离织物和PTFE隔膜薄膜及聚酯吸收性羊毛状物。通过借助真空灌注施用纤维增强外层来由模制品制造面板。将两层Quadrax玻璃粗纱(E玻璃SE1500,OCV;织物:Saertex,在每种情况下具有1200g/m2的各向同性层压材料[0°/-45°/90°45°])分别施用到(纤维增强)泡沫的上侧和下侧。将分离织物和流动助剂安装在玻璃粗纱的两侧。随后,使该结构配备有用于树脂体系的开口和用于排空的开口。最后,在整个结构上施用真空膜并用密封带密封,并且将整个结构排空。该结构在电加热阶段用玻璃表面制造。
所使用的树脂体系是胺-固化环氧化物(树脂:BASF Baxxores 5400,固化剂:BASFBaxxodur 5440,混合比例和进一步处理根据数据表)。在两种组分混合后,将树脂在低至20毫巴下排空10分钟。在23±2℃的树脂温度下,对预热结构进行灌注(阶段温度:35℃)。通过随后以0.3K/min的温度梯度从35℃至75℃,并在75℃下恒温固化6小时,可以制造由模制品和玻璃纤维增强外层组成的面板。所述面板可毫无困难地制造。此外,支撑部位可以阻止在用于真空灌注制造中纤维的拉出。此外,更好的纤维排列和由此更好的耐久性确保了后续使用中的机械应力。
Claims (15)
1.由泡沫制成的模制品,所述泡沫包含至少两个相互粘结的泡沫段,其中至少一根纤维(F)在模制品内存在有纤维区域(FB2)并被泡沫包围,同时纤维(F)的纤维区域(FB1)从模制品的第一侧突出,且纤维(F)的纤维区域(FB3)从模制品的第二侧突出,其中纤维(F)已经通过包括以下步骤a)至f)的方法部分地被引入:
a)任选地将至少一层(S2)施用到泡沫的至少一侧,
b)对于每根纤维(F)在泡沫和任何层(S2)中产生一个孔,该孔从泡沫的第一侧延伸到第二侧并穿过任何层(S2),
c)在泡沫的第二侧上提供至少一根纤维(F),
d)使针从泡沫的第一侧穿过孔到泡沫的第二侧,并使针穿过任何层(S2),
e)在泡沫的第二侧上,将至少一根纤维(F)固定在针上,以及
f)将针与纤维(F)一起通过孔返回,使得纤维(F)在模制品内存在有纤维区域(FB2)并被泡沫包围,同时纤维(F)的纤维区域(FB1)从模制品的第一侧或从任何层(S2)突出,且纤维(F)的纤维区域(FB3)从模制品的第二侧突出。
2.权利要求1的模制品,其中
i)至少两个相互粘结的泡沫段已通过粘合剂粘结和/或焊接而彼此粘结,并且优选地,模制品的泡沫的所有相互粘结的泡沫段已通过热焊接和/或粘合剂粘结而彼此粘结,和/或
ii)单个泡沫段的长度(x方向)为至少2mm、优选20至8000mm、更优选100至400mm,宽度(y方向)为至少2mm、优选5至4000mm、更优选25至2500mm,且厚度(z方向)为至少2mm、优选至少5mm、更优选至少25mm、最优选30至80mm,和/或
iii)单个泡沫段具有板坯形状,和/或
iv)单个泡沫段的长度(x方向)与厚度(z方向)之比为至少5、优选至少10、更优选至少20、最优选20至500,和/或
v)单个泡沫段的宽度(y方向)与厚度(z方向)之比为至少3、优选至少5、更优选至少10、最优选10至250,和/或
vi)至少一根纤维(F)穿过泡沫的两个相互粘结的泡沫段之间的至少一个粘结表面,并且优选地,所有纤维(F)的至少20%穿过泡沫的两个相互粘结的泡沫段之间的至少一个粘结表面,更优选所有纤维(F)的至少50%,和/或
vii)至少一根纤维(F)以≥20°、优选≥35°、尤其是40°至90°的角度δ部分地或完全地穿过两个相互粘结的泡沫段之间的至少一个粘结表面,和/或
viii)至少两个相互粘结的泡沫段之间的至少一个粘结表面、优选所有粘结表面的厚度为至少2μm、优选至少5μm、更优选20至2000μm、最优选50至800μm,和/或
ix)至少两个相互粘结的泡沫段之间的至少一个粘结表面、优选所有粘结表面的厚度大于相互粘结的泡沫段的平均泡孔壁厚的总和,优选比泡孔壁厚度总和大2至1000倍且更优选大5至500倍。
3.权利要求1或2的模制品,其中泡沫的泡沫段由模制泡沫、挤出泡沫、反应性泡沫和/或母料泡沫制成,优选由挤出泡沫制成,尤其是以包括以下步骤的方法所制备的挤出泡沫:
I)在挤出机中提供聚合物熔体,
II)将至少一种发泡剂引入到步骤I)中提供的聚合物熔体中,以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通过至少一个模具孔从挤出机挤出到较低压力的区域中,并且使可发泡聚合物熔体膨胀以获得膨胀泡沫,
IV)通过使膨胀泡沫通过成形工具而将来自步骤III)的膨胀泡沫定型,以获得挤出泡沫,
V)任选地将步骤IV)中获得的挤出泡沫进行材料去除处理,
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)期间施用至膨胀泡沫和/或在步骤IV)期间施用至膨胀泡沫,和/或
iv)任选地将至少一层(S2)在步骤IV)期间和/或直接在步骤IV)之后施用至挤出泡沫。
4.权利要求1至3中任一项的模制品,其中所述泡沫段包含泡孔,其中
i)至少两个泡沫段、优选所有泡沫段的至少50%、优选至少80%且更优选至少90%的泡孔是各向异性的,和/或
ii)至少两个泡沫段、优选所有泡沫段的至少50%、优选至少80%且更优选至少90%的泡孔的最大尺寸(a方向)与最小尺寸(c方向)之比为≥1.05、优选1.1至10、特别优选1.2至5,和/或
iii)基于其最大尺寸(a方向),至少两个泡沫段、优选所有泡沫段的至少50%、优选至少80%且更优选至少90%的泡孔以相对于模制品的厚度方向(d)成≤45°、优选≤30°且更优选≤5°的角度γ排列。
5.权利要求1至4中任一项的模制品,其中所述泡沫的泡沫段基于至少一种选自以下的聚合物: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,
优选地,聚合物选自以下: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混合物,
更优选地,聚合物为聚苯乙烯,聚苯乙烯和聚(2,6-二甲基苯醚)的混合物、苯乙烯-顺丁烯二酸酐聚合物和苯乙烯-丙烯腈聚合物的混合物,或苯乙烯-顺丁烯二酸酐聚合物(SMA),
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-卤代苯乙烯、环烷基化苯乙烯、丙烯腈、丙烯酸酯、异丁烯酸酯、N-乙烯基化合物、顺丁烯二酸酐、丁二烯、二乙烯基苯和二丙烯酸丁二醇酯。
6.权利要求1至5中任一项的模制品,其中泡沫的所有泡沫段均基于相同的聚合物。
7.权利要求1至6中任一项的模制品,其中
i)纤维(F)是单纤维或纤维束,优选纤维束,和/或
ii)纤维(F)是有机、无机、金属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,和/或
iii)纤维(F)以纤维束的形式使用,每束的单纤维的数量在玻璃纤维的情况下为至少10根、优选为100至100 000根、更优选为300至10 000根且在碳纤维的情况下为1000至50000根,并且特别优选在玻璃纤维的情况下为500至5000根且在碳纤维的情况下为2000至20000根,和/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%、优选2%至40%且更优选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%且更优选40%至90%,和/或
v)纤维(F)已经以相对于模制品的厚度方向(d)成0°至60°、优选0°至50°、更优选0°至15°或10°至70°、特别是30°至60°、更优选30°至50°、甚至更优选30°至45°且特别是45°的角度α引入到泡沫中,和/或
vi)在模制品中,纤维(F)的纤维区域(FB1)从其突出的模制品的第一侧与纤维(F)的纤维区域(FB3)从其突出的模制品的第二侧相对,和/或
vii)模制品包含多根纤维(F),优选为纤维束,和/或包含大于10根纤维(F)或纤维束/m2,优选大于1000根/m2,更优选4000至40 000根/m2。
8.一种面板,其包含至少一个权利要求1至7中任一项的模制品和至少一个层(S1)。
9.权利要求8的面板,其中层(S1)包含至少一种树脂,该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,并且该树脂特别为胺固化环氧树脂、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的树脂。
10.权利要求8或9的面板,其中层(S1)还包含至少一种纤维材料,其中
i)纤维材料包含一层或多层短切纤维、纤维网、稀松布、编织物和/或织物形式,优选为稀松布或织物形式,更优选为具有稀松布或织物的基重为150至2500g/m2的稀松布或织物形式的纤维,和/或
ii)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。
11.权利要求8至10中任一项的面板,其中所述面板具有两层(S1),并且两层(S1)分别安装在模制品的与模制品的相应另一侧相对的一侧上。
12.权利要求8至11中任一项的面板,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)在模制品的至少一侧与至少一层(S1)之间所述面板具有至少一层(S2),所述层(S2)优选由二维纤维材料或聚合物膜组成,更优选由纤维网、稀松布或织物形式的玻璃纤维或碳纤维组成。
13.用于制造权利要求1至7中任一项的模制品的方法,其包括通过步骤a)至f)将至少一根纤维(F)部分引入到泡沫中:
a)任选地将至少一层(S2)施用到泡沫的至少一侧,
b)对于每根纤维(F)在泡沫和任意层(S2)中产生一个孔,该孔从泡沫的第一侧延伸到第二侧并穿过任意层(S2),
c)在泡沫的第二侧上提供至少一根纤维(F),
d)使针从泡沫的第一侧穿过孔到泡沫的第二侧,并使针穿过任意层(S2),
e)在泡沫的第二侧上将至少一根纤维(F)固定在针上,以及
f)将针与纤维(F)一起通过孔返回,使得纤维(F)在模制品内存在有纤维区域(FB2)并且被泡沫包围,同时纤维(F)的纤维区域(FB1)从模制品的第一侧或从任意层(S2)突出,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)。
14.用于制造权利要求8至12中任一项的面板的方法,其包括制备、施用并固化至少一层以反应性粘性树脂形式的层(S1)至权利要求1至7中任一项的模制品上,优选通过液体浸渍方法,更优选通过压力或真空辅助浸渍法,尤其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。
15.权利要求1至7中任一项的模制品或权利要求8至12中任一项的面板用于风力涡轮机中的转子叶片、在运输领域、建筑领域、汽车制造、造船、铁路车辆结构、容器结构、卫生设施和/或航空航天中的用途。
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CN111520292A (zh) * | 2020-03-25 | 2020-08-11 | 株洲时代新材料科技股份有限公司 | 一种增强夹芯材料抗压性能的方法 |
CN111520292B (zh) * | 2020-03-25 | 2021-10-26 | 株洲时代新材料科技股份有限公司 | 一种增强夹芯材料抗压性能的方法 |
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JP6826982B2 (ja) | 2021-02-10 |
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BR112017013538B1 (pt) | 2021-11-30 |
RU2017126250A3 (zh) | 2019-05-14 |
BR112017013538A2 (pt) | 2018-03-06 |
RU2017126250A (ru) | 2019-01-24 |
EP3237508B1 (de) | 2020-04-22 |
US20170361545A1 (en) | 2017-12-21 |
RU2705089C2 (ru) | 2019-11-01 |
CN107250228B (zh) | 2021-03-16 |
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EP3237508A1 (de) | 2017-11-01 |
WO2016102244A1 (de) | 2016-06-30 |
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