CN105579214A - 使用纤维结构的切屑的方法 - Google Patents

使用纤维结构的切屑的方法 Download PDF

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CN105579214A
CN105579214A CN201480052118.7A CN201480052118A CN105579214A CN 105579214 A CN105579214 A CN 105579214A CN 201480052118 A CN201480052118 A CN 201480052118A CN 105579214 A CN105579214 A CN 105579214A
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thin slice
polymer melt
fiber
fabric
polymer
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M·沙伊比茨
H·赫斯
J·克勒梅
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BASF SE
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Abstract

本发明提供一种使用纤维结构的切屑的方法，包括以下步骤：(a)将切屑切成薄片，(b)将薄片掺入聚合物熔体中，(c)捏合含有薄片的聚合物熔体，从而将薄片分解成单独的纤维，(d)将含有掺入的纤维的聚合物熔体成型为中间制品。

Description

使用纤维结构的切屑的方法
本发明涉及一种使用织物切屑(fabriccuttingscrap)的方法。
织物是例如由在连续股状的复合材料的制造中使用的纤维编织、织造或铺设的织物。
连续股状的复合材料通常通过将织物嵌入模具中，然后向模具中注入模制聚合物(例如热固性聚合物或热塑性聚合物)而形成。所用的织物例如可为编织物、针织物或无纬织物。可叠加两层以上相对彼此旋转或不旋转的织物。
尤其当织物采用通过辅助线束支撑在一起的织造纤维、针织纤维或平行纤维的形式时，它们的形状与待生产的组件的形状不符。因此，首先需要生产组件的织物必须切割成一定尺寸。在该过程中产生的切屑不能用于生产其他连续的股状增强组件。因此，切屑通常被送去处理掉。特别地，当前碳纤维切屑通过焚化而处理掉，但由于碳纤维的高成本，这是不希望的。
除了热回收外，DE-A102009023529公开了这样一种方法：首先将未浸染的碳纤维的纤维复合材料碎屑切割成确定纤维长度的片段；这些片段被解离至纤维个体化的程度，并将所得的随机形式的碳纤维重组成纺成连续的纱线的纤维非织造网或纤维梳棉网(fibrouscardweb)。此处产生的具体问题是，通过聚芳基酰胺纤维或芳纶纤维进行的这种重复撞击(例如在锤式粉碎机中)分解成单根纤维的基本无损的再利用不能用于碳纤维。具体而言是因为碳纤维的脆性，所以该方法不能粉碎成可计量的或极短的纤维，因此不能实现用这些纤维充分加固聚合物部件。在DE-A102009023529中描述的该方法的一个具体缺点是要求保护可计量的材料需要巨大的支出。在现有方法中不能直接使用切割片段。
因此，本发明解决的问题是提供一种不具有现有技术缺点的使用织物切屑的方法。
该问题通过一种使用织物切屑的方法来解决，所述方法包括以下步骤：
(a)将切屑切成薄片，
(b)将薄片掺入聚合物熔体中，
(c)将聚合物熔体与薄片捏合，从而将薄片分解成单独的纤维，
(d)将聚合物熔体和掺入的纤维模塑成中间制品。
将碎屑切成薄片提供了一种将单独的薄片掺入聚合物熔体中的简单方法。由于碎屑被切割成薄片，纤维之间原来的键不足以使薄片保持其形式，因此碎屑在掺入和捏合至聚合物熔体中的过程中被分解成单独的纤维。这使得可以使用薄片生产相当于短切股状材料的纤维增强的聚合物。
在一个优选的实施方案中，产生切屑的织物为通常由连续的股状纤维制造的织造物、无纬织物、针织物、穗带、非织造物或垫子。有用的织造物包括可由连续的股状纤维得到的任何织造物。还可以使用任何期望的针织物。用于本发明目的的无纬织物为单独的纤维平行排列的织物。在此，所述织物也可由两股以上构成，而单股可彼此平行排列或以相对彼此任意期望的角度缠绕。
当纤维为无纬织物的形式时，单独平行纤维例如通过纤维或聚合物细丝互相连接。此处的互相连接采用例如合成纤维或连续股状纤维缝合的线缝的形式。该线缝优选使用合成纤维，例如聚合物纤维形成。此处的线缝例如包括垂直于无纬纤维织物的底线(underthread)和以预定间隔穿过纤维缝合并围绕底线的顶线(overthread)。
所用织物可包含已用上浆组合物预处理过的纤维，或未处理的纤维。所述织物还可以已用聚合物，特别是热塑性聚合物浸透过。然而，优选未处理的纤维或至多使用上浆组合物预处理过的纤维。
特别是当切屑的纤维未被处理时，优选在切屑已切成薄片且在薄片掺入聚合物熔体前，使用上浆组合物处理薄片。可使用本领域技术人员已知的任何上浆组合物。使用上浆组合物处理具有改善聚合物至纤维的粘附性的优点，并因此影响了通过本发明方法获得的纤维增强聚合物性能的整体改善。特别是当使用单独纤维和/或当薄片由无纬纤维织物切割而来时，纤维的预处理是有利的。特别优选用粘合剂浸透的纤维，以将其转变成可计量的形式。薄片是可计量形式的一个实例。纤维薄片对单根纤维来说是有利的，因为它们能更轻易地通过常规的供料装置掺入用于捏合聚合物熔体和薄片的机器，例如挤出机或注塑机中。
生产被切成薄片的切屑的织物可包含任何所期望的已知材料的纤维。用于纤维的常规材料为，例如：玻璃纤维、碳纤维、芳纶纤维、矿物纤维或聚合物纤维。本发明的方法特别适于由碳纤维制造的织物的切屑，对其使用现有的再循环方法是不明智的。
当前，包含增强形式的碳纤维和碳纤维织物切屑的聚合物被送去进行热回收。但这意味着高价值材料的巨大浪费，因为其在热回收中被焚化而不能用于其最初的目的。本发明的方法为碳纤维提供了一种使用切屑生产增强聚合物的特别方法。
将切屑切成薄片可例如用刀片(如模切刀片或辊刀)、模切格子(diecuttinglattice)或激光来实现。同样可使用数控刀具(CNCcutter)将切屑切成薄片。特别优选使用模切格子或激光。通常使用将织物转变成生产连续股状增强模制品的形式同样使用的相同装置来切割薄片。为此，需要的是全部采用，例如模切格子或刀片的形式，从而使其能够用于切割薄片。
切割待生产的纤维增强组件大小的同时也可将切屑切成薄片。应当理解的是，还可以在单独的第二步骤中将切屑切割成薄片。同时进行的织物切割和碎屑切割使用允许这种切割的工具而实现。于是必须使用适当设计的模切刀片或模切格子用于该目的。但是，在该情况下优选使用数控刀具。
当在单独的步骤中将切屑切割成薄片时，可使用任何期望的适合切割尺寸的工具，在这种情况下上述切割成一定尺寸的工具是特别适合的。当在单独的步骤中将切屑切割成薄片时，切屑可被切割成单层的薄片或具有两层以上叠加层的切屑的薄片。可同时切割的层的最大数目取决于所用的工具。出于效率的原因，优选一次切割尽可能多的层，条件是当用激光切割时，这不会例如因为需要放慢向前进料的速度，导致总的切割时间增加。
织物切屑切割成的薄片的边缘长度优选在10至50mm范围内，特别是在优选10至20mm范围内。此处的边缘长度还取决于将薄片掺入聚合物熔体中所用的机器。
当将薄片掺入聚合物熔体时，单个的薄片分解成单独的纤维，然后将单独的纤维掺入聚合物熔体中。根据所用薄片的大小和在混合薄片的装置中的剪切效应，一些纤维将会破碎，因而由此得到的纤维增强聚合物的性能与短切股状增强聚合物的性能相符合。
特别地，纤维断裂是由于碳纤维的脆性和在螺杆柱塞机中的加工造成的，其中螺杆的旋转是剪切材料的原因。
将薄片掺入或捏合进聚合物熔体中的合适的装置特别地为螺杆柱塞机，例如注塑机或挤出机，特别是挤出机。在常用于掺入纤维的位置向其中添加薄片。掺入纤维的位置通常位于进料区的下游，所述进料区是加入螺杆柱塞机中的聚合物已完全熔化的区域。当螺杆柱塞机中已供入聚合物熔体时，薄片的进料口可直接位于紧跟聚合物熔体进料口的位置。由于通常向螺杆柱塞机中供入聚合物颗粒，即固体形式的塑料，所以在加入薄片之前首先需要熔化聚合物。将薄片加入聚合物熔体提供熔体和薄片的更均匀的混合，并因此使得所得的单独的纤维在聚合物熔体中更均匀的分布。
当所用的螺杆柱塞机为挤出机时，不仅可以使用单螺杆挤出机，还可以使用多螺杆挤出机，例如双螺杆挤出机。特别优选使用双螺杆挤出机，因为其特别地与单螺杆挤出机相比具有更好的混合效果。双螺杆挤出机还能更容易地加入填料，且可以用可变的填充物来操作，还产生良好的液化作用，并且可以实现对产品性能更好地控制。此外，不像单螺杆挤出机，双螺杆挤出机具有非常好的自清洁性能。
薄片通过优选包含进料螺杆的进料口引入螺杆柱塞机，例如挤出机。进料螺杆提供将薄片加入聚合物熔体中的均匀速率。没有进料螺杆，例如通过进料孔(feedaperture)加入薄片，带来的风险是，薄片将不被聚合物熔体吸收或薄片仅偶然地共同进入聚合物熔体中，因此纤维在聚合物中的比例会非常低。
进料螺杆能控制加入聚合物熔体中薄片的量。特别地，进料螺杆可用于实现薄片的强制进料，使得在聚合物熔体中达到最高达50重量％比例的薄片，即纤维。接着计量加入聚合物熔体中的薄片即纤维的比例优选在1至50重量％范围内，特别是在1至40重量％范围内。
中间制品中纤维的长度首先取决于螺杆柱塞机中纤维的剪切，其次取决于聚合物熔体切出的颗粒材料标注的尺寸。最大的纤维长度对应于单个颗粒最大的纵向长度。如果期望更长的纤维，不仅需要切割具有更大边缘长度的薄片，还要生产更大的颗粒。所述颗粒优选为圆柱形，且其最大长度通常为圆柱的高度。或者，还可以选择更大的直径和更小的高度。但因为纤维由于聚合物熔体的供入而相对于造粒模具中孔的轴线基本上平行地排列在轴线方向上，因此通常颗粒的轴向长度决定了最大的纤维长度。
掺入薄片的聚合物可为热塑性聚合物、热固性聚合物或弹性聚合物。特别优选聚合物熔体包含热塑性聚合物，且最优选聚合物熔体为热塑性聚合物的熔体。
热塑性聚合物优选选自：聚对苯二甲酸丁二醇酯(PBT)、聚对苯二甲酸乙二醇酯(PET)、聚甲醛(POM)、聚酰胺(PA)、聚丙烯(PP)、聚乙烯(PE)、聚醚砜(PES)或其两种以上的混合物。除上述热塑性聚合物以外，还可使用任意其他期望的热塑性聚合物。
通过本发明方法获得的中间制品更优选为颗粒材料。但除颗粒材料外，中间制品还可采用片或挤出物的形式。当中间制品为包含纤维的颗粒材料时，该颗粒材料以颗粒的通常形式通过将聚合物熔体强制通过造粒模具并由切粒刀切成颗粒来生产。进行该操作的一种可能的方式是，首先生产聚合物挤出物，然后待其冷却后切成颗粒。或者，常规地，将强制通过造粒模具的聚合物直接弦切。该切割可在空气中进行，在这种情况下，切下的颗粒优选落入冷却液中并凝固。水是合适的冷却液的一个实例。或者，水下造粒也是可以的，在这种情况下，聚合物熔体被强制通过造粒模具进入冷却液中，并直接被弦切成颗粒。无论哪种情况，颗粒和冷却液一同被排出，然后除去冷却液并干燥。
由此得到的颗粒材料可进一步以任何期望方式进行加工，从而将塑料颗粒加工成最终制品。例如，该塑料颗粒可通过挤压或注塑成型来塑造成最终制品。此处，可使用任何期望的注塑机或挤压机，条件是其对生产最终制品有用，更具体而言，其适于加工纤维增强的塑料。
可由通过本发明方法得到的颗粒材料所得到的模制品包括所有具体的在几何上要求的形状，这些形状也可以用市售可得的纤维增强热塑性塑料，例如气缸盖垫圈、涡轮增压器的进气歧管、开关壳体来得到。
实施例
为了生产纤维增强的尼龙，用碳纤维片的计量单元改装市售可得的双螺杆挤出机。为此目的，将具有安装于其基部的下联接轴的原料储存容器安装在双螺杆挤出机侧面进料上方的中心处。
为了生产用20重量％的碳纤维增强的尼龙-6,6，第一步是用数控刀具将无纬织物连续股状碳纤维垫碎屑切割成20×20mm的薄片。然后将由此切得的薄片引入双螺杆挤出机胶料进料(sizefeed)上方的原料储存容器中，并由侧面进料按重量计量进入尼龙-6,6的熔体中。将由此得到的材料在挤出机后直接进行造粒。
在进一步的处理步骤中，将由此得到的材料在注塑机上生产测试样品。在表1中示出在测试样品上测得的数值和在用20重量％的短切碳纤维增强的市售可得的尼龙(购自BASFSE的A3WC4)的测试样品上测得的数值。“实施例”是指由根据本发明获得的尼龙形成的测试样品的数值，而“对照例”是指由市售可得的尼龙形成的测试样品的数值。
数值的对比表明，其性能基本上相当于用短切玻璃纤维增强的常规聚合物的性能。
表1：由本发明方法得到的纤维增强的尼龙-6,6和市售可得的纤维增强的尼龙-6,6的特性值

Claims (11)

1.一种使用织物切屑的方法，所述方法包括以下步骤：
(a)将切屑切成薄片，
(b)将薄片掺入聚合物熔体中，
(c)捏合聚合物熔体和薄片，从而将薄片分解成单独的纤维，
(d)将聚合物熔体和掺入的纤维模塑成中间制品。
2.权利要求1的方法，其中织物为来自连续股状纤维的织造物、铺设物或针织物。
3.权利要求1或2的方法，其中织物由碳纤维制造。
4.权利要求1至3中任一项的方法，其中薄片在掺入聚合物熔体之前用上浆组合物进行处理。
5.权利要求1至4中任一项的方法，其中使用刀片、模切格子或激光将切屑切成薄片。
6.权利要求1至5中任一项的方法，其中使用螺杆柱塞机掺入薄片并捏合聚合物熔体和薄片。
7.权利要求6的方法，其中螺杆柱塞机为挤出机。
8.权利要求7的方法，其中挤出机包括具有进料螺杆的进料口，以将薄片掺入聚合物熔体中。
9.权利要求1至7中任一项的方法，其中聚合物熔体包含热塑性聚合物。
10.权利要求9的方法，其中热塑性聚合物选自：聚对苯二甲酸丁二醇酯、聚对苯二甲酸乙二醇酯、聚甲醛、聚酰胺、聚丙烯、聚乙烯、聚醚砜或其两种以上的混合物。
11.权利要求1至10中任一项的方法，其中中间制品为包含纤维的颗粒材料。
CN201480052118.7A 2013-09-24 2014-09-12 使用纤维结构的切屑的方法 Pending CN105579214A (zh)

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