CN101218079B - 用于提高芳族聚酰胺短切纤维的长丝粘结性的方法 - Google Patents
用于提高芳族聚酰胺短切纤维的长丝粘结性的方法 Download PDFInfo
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Abstract
本发明涉及一种提高芳族聚酰胺短切纤维丝粘结性的方法，包括如下步骤：用膜形成粘合剂浸渍纤维；干燥纤维；可选地向纤维涂用整理剂；以及，将纤维短切成长1-16mm的纤维段；其特征在于，在用膜形成粘合剂浸渍纤维之前对纤维进行加捻工序，以获得捻度水平为10-150tpm的纤维；特征还在于，纤维的短切在旋转式短切机中进行。
Description
技术领域
本发明涉及一种用于提高芳族聚酰胺短切纤维的长丝粘结性的方法。
背景技术
填充有芳族聚酰胺纤维(通常高达20％)且为颗粒状的热塑性预复合物常用作例如通过注射成型工艺生产具有增强的抗磨损性能的复合制品(如齿轮、轴承)的原料。通过将热塑性基质材料切片与芳族聚酰胺短切纤维混合并经由熔融挤出工艺制备所述预复合物。为此，分别将热塑性切片和芳族聚酰胺短切纤维定量供入挤出机的进料口。向挤出机中喂入纤维会严重问题：形成纤维桥结和纤维团块，从而妨碍向挤出机中平滑快速地引入。看起来像是不再粘着在短切纤维段中的那些单个长丝聚结成绒球，从而产生团块、桥结并堵塞输送系统。
发明内容
因此，本发明的目的在于提供一种获得不具有上述缺点的短切纤维的方法。因此本方法提供了颗粒状短切纤维、即其中一长丝粘结性增强从而表现出似乎该纤维是一大单丝的性能的纤维。但是，不能通过涂用经改良的粘合剂或类似物来减少上述缺点，因为这并不能从本质上增强丝束粘合性。
为此，本发明提供了一种提高芳族聚酰胺短切纤维的长丝粘结性的方法，包括如下步骤：用膜形成粘合剂浸渍纤维；干燥纤维；可选地向纤维涂用整理剂；以及，将纤维短切成长1-16mm的纤维段；其特征在于，在用膜形成粘合剂浸渍纤维之前对纤维进行加捻工序，以获得捻度水平为10-150tpm的纤维；特征还在于，纤维的短切在旋转式短切机中进行。
令人惊讶地发现，在为制备短切纤维而进行的旋转式短切之前实施加捻步骤从本质上增强了长丝粘结性，从而能够完全或几乎完全防止自由长丝聚结成绒球。因此，本方法的效果在于显著增大了纤维材料的堆积密度。增大堆积密度相当于使材料能更容易地喂入挤出机中。
对于芳族聚酰胺纤维而言，本发明的方法尚不为人知。根据US5,227,238，碳纤维被短切并最优选提供成10-20捻每米，以获得集束度更佳的短切碳纤维。但是，US 5,227,238并未公开使用旋转式短切机来增加堆积密度。
根据本发明将芳族聚酰胺纤维加捻成捻度水平为至少10tpm(捻回每米)、但不超过150tpm，所述加捻是纤维领域中极为常见的工艺，对于本领域的技术人员而言无需进一步说明。捻度水平为20-100tpm、最优选为30-80tpm时效果更好。这些经加捻的纤维大致呈圆形，该几何结构通过纤维上的浆料进行固定，切断后将获得圆形或椭圆形(横截面)短切纤维，而不是使用现有技术的情况下的扁平短切纤维。这些圆形或椭圆形短切纤维被认为还有利于简化对这些纤维的操作。
在作为最终获得经改良的短切纤维的主要步骤的加捻步骤之后，用膜形成粘合剂和可选的涂层整理剂处理纤维。所述粘合剂可进一步增强丝间粘结，并且，所述粘合剂应该是一种在挤出机中熔融的膜形成聚合物。优选地，所述粘合剂是水可溶性的或水可分散性的，例如是聚氨基甲酸酯和/或磺化聚酯树脂。
适宜的聚酯的示例是磺化二羧酸、二羧酸和二元醇衍生的聚合物。优选衍生自二甲基磺基间苯二甲酸钠、间苯二甲酸和乙二醇的聚酯。这种产品可以商品名Eastman
LB-100提供。适宜的聚氨基甲酸酯的示例是聚醚-聚氨基甲酸酯或聚酯-聚氨基甲酸酯分散体，可分别以商品名Alberdingk
U400N和ImpranilDLF提供。粘合剂的适宜的量在1.5-12wt.％之间，优选为2.0-9wt.％，更优选为2.5-6wt.％。当粘合剂作为水溶液或水分散体被涂用时，在涂用粘合剂之后，应例如通过转鼓式干燥器、空气干燥器等对纤维进行干燥。
如果使用，涂层整理剂是减少被处理的纱和短切纤维分别对切断装置的引导辊和到挤出机的输送系统的金属部件的摩擦力的低特性粘度的油。优选地，涂层整理剂是用量为0.05-3wt.％、更优选为0.1-1wt.％的酯油。适宜的油的示例是硬脂酸2-乙基己酯、棕榈酸2-乙基己酯、月桂酸正丁酯、辛酸正辛酯、硬脂酸丁酯或其混合物。更优选的酯油是可以商品名
245提供的硬脂酸2-乙基己酯和棕榈酸2-乙基己酯的混合物。
将经粘合剂处理、干燥并可选地还涂有整理剂的纤维短切成1-16mm、优选为2-12mm、更优选为3-10mm的纤维段。利用旋转式短切机进行所述短切。旋转式短切机具有其它优点，即更高效、过程更经济且产生更少废料或不产生废料。尽管适于短切芳族聚酰胺纤维的任何其它常见的短切机如铡刀式短切机也能使堆积密度增大，却不能实现本发明的方法的极高的堆积密度。
还发现，通过使用低线密度的纤维可进一步改善加捻和旋转式短切的效果。在把纤维短切成短段、优选为4mm或更小时，这种额外的效果特别显著。因此，优选使用线密度小于2000dtex的纤维，并且，优选将纤维短切成长度小于4mm。
可根据本发明的方法处理的纤维包括任何芳族聚酰胺纤维、特别是连续的初生纤维(spun fiber)和牵切纱(stretch broken yarn)。纱纤度对于本发明并不重要，但通常在800-8050dtex之间、更优选在1200-4830dtex之间。适宜的芳族聚酰胺纤维包括间和对芳族聚酰胺纤维，如
纤维[聚-(间-亚苯基间苯二酰胺)；MPIA]、
纤维[聚(对-亚苯基对苯二酰胺)；PPTA]和
纤维[对亚苯基对苯二酰胺和3，4’-氧二亚苯基对苯二酰胺的共聚物]。最通常使用纤维。
经根据本发明的方法处理的纤维表现出强的丝间粘合性，即短切成小段的纤维不易于分成单独的长丝。因此，本发明的短切纤维具有高的堆积密度，并易于定量供给和分散在挤出机中，以便与热塑性材料如聚酰胺、聚甲醛、聚碳酸酯、聚对苯二甲酸丁二醇酯等一起制备复合物。
本发明在下面的非限制性的说明性示例中进一步说明并显示出本发明的优点。
具体实施方式
示例1
用粘合剂(Eastman LB-100，Eastman化工公司，Kingsport，美国)浸渍芳族聚酰胺纤维(PPTA，Twaron
)3360dtex、干燥、并用涂层整理剂(LW 245，Cognis，Düsseldorf，德国)处理。然后，将纤维在Neumag旋转式短切机中以100mpm(米每分钟)短切成6mm的纤维段，测定堆积密度(短切纤维A大致扁平；根据现有技术)。
堆积密度测定如下：
所需仪器：
容量为1000ml的圆形铝制量杯(内径10cm，高12.7cm)；
天平(精度0.01克)
直尺
称量铝制量杯(a克)并将其置于试验台上。从约10cm的高度向铝制量杯中填充短切纤维。加入尽可能多的纤维直到形成一纤维堆。用尺掠过量杯顶部而除去该纤维堆。称量填充后的铝制量杯(b克)。在测定期间应避免摇动量杯或挤压短切纤维。短切纤维的堆积密度为(b-a)克。测试两次，平均值即为纤维试样的堆积密度。
在示例中使用了参量“堆积密度比”。在示例1中，堆积密度比是指(短切纤维试样的堆积密度×100)与(由未经加捻的纱制得的短切纤维的堆积密度)之比。在示例2中，堆积密度比是指(短切纤维试样的堆积密度×100)与(由铡刀机短切的纱制得的短切纤维的堆积密度)之比。因此，由未经加捻的纱制得的短切纤维的堆积密度比(示例1)和由铡刀机短切的纱制得的短切纤维的堆积密度比(示例2)设定为“100”。
重复所述过程，但是，纤维在浸渍之前经过加捻(短切纤维I为椭圆形或大致圆形；根据本发明)。结果如表1所示。
表1
| A | I | |
| 捻度水平(tpm) | 0 | 50 |
| 粘合剂(％) | 4.5 | 4.5 |
| 干燥方法 | 烘箱 | 烘箱 |
| 整理剂(％) | 0.7 | 0.7 |
| 短切(线数(no.of threads)) | 2 | 2 |
| 堆积密度比 | 100 | 117 |
经加捻的短切纤维的堆积密度高于未经加捻的纤维的堆积密度。因此，经加捻的材料能更容易、更快速且无堵塞危险地被用于向挤出机进料。
示例2
用粘合剂Eastman LB-100浸渍经加捻的芳族聚酰胺纤维(PPTA，Twaron
)3360dtex、干燥并使用LW 245作为涂层整理剂进行处理。将纤维短切成6mm的短切纤维。一部分纤维使用Pierret铡刀式短切机以1.2mpm进行短切(短切纤维B；比较例)，另一部分纤维使用Neumag旋转式短切机以120mpm进行短切(短切纤维II；本发明)。短切纤维B和II均为椭圆形或大致圆形。结果如表2所示，结果表明，使用旋转式短切机可生产出堆积密度较高且产量较高的短切纤维。
表2
| B | II | |
| 捻度水平(tpm) | 60 | 60 |
| 粘合剂(％) | 4.0 | 4.0 |
| B | II | |
| 干燥方法 | 烘箱 | 烘箱 |
| 整理剂(％) | 0.6 | 0.6 |
| 短切(丝束，ktex) | 806 | 17 |
[0033]
| 产量(Kg/小时) | 58 | 122 |
| 堆积密度比 | 100 | 116 |
示例3
用粘合剂Eastman LB-100浸渍经加捻的芳族聚酰胺纤维(PPTA，Twaron)3360dtex(III)和1680dtex(IV)、干燥并使用LW 245作为涂层整理剂进行处理。将纤维短切成短切纤维。使用Neumag NMC 290H旋转式短切机得到长度为1.5mm和3.3mm的短切纤维。使用Fleissner旋转式短切机得到长度为6mm的短切纤维。结果表明，使用具有较低线密度的经加捻的进料纱可制得堆积密度较高的短切纤维。
表3
Claims (9)
1.一种提高芳族聚酰胺短切纤维丝粘结性的方法，包括如下步骤：用膜形成粘合剂浸渍纤维；干燥纤维；以及，将纤维短切成长1-16mm的纤维段；其特征在于，在用膜形成粘合剂浸渍纤维之前对纤维进行加捻工序，以获得捻度水平为10-150tpm的纤维；特征还在于，纤维的短切在旋转式短切机中进行。
2.根据权利要求1所述的方法，其特征在于，该方法还包括向纤维涂用整理剂。
3.根据权利要求1所述的方法，其特征在于，所述捻度水平为20-100tpm。
4.根据权利要求1所述的方法，其特征在于，所述捻度水平为30-80tpm。
5.根据权利要求1所述的方法，其特征在于，所述膜形成粘合剂是水可溶性或水可分散性膜形成粘合剂。
6.根据权利要求5所述的方法，其特征在于，所述膜形成粘合剂是聚氨基甲酸酯或聚酯、或它们的混合物。
7.根据权利要求1-6中任一项所述的方法，其特征在于，所述纤维是聚(对-亚苯基对苯二酰胺)纤维。
8.根据权利要求1-6中任一项所述的方法，其特征在于，所述纤维是对亚苯基对苯二酰胺和3，4’-氧二亚苯基对苯二酰胺的共聚物。
9.根据权利要求1-6中任一项所述的方法，其特征在于，所述纤维的线密度小于2000dtex，所述纤维短切成长度小于4mm。
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| PCT/EP2006/006419 WO2007006438A1 (en) | 2005-07-08 | 2006-07-01 | Method for improving filament cohesiveness of chopped aramid fiber |
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| EP2185634B1 (en) * | 2007-10-04 | 2010-12-01 | Invista Technologies S.à.r.l. | Reinforcing fiber bundles for making fiber reinforced polymer composites |
| RU2477687C2 (ru) * | 2007-11-30 | 2013-03-20 | Тейджин Арамид Б.В. | Гибкая сплошная лента из комплексной нити и способ ее изготовления |
| JP5178295B2 (ja) * | 2008-04-16 | 2013-04-10 | 帝人株式会社 | 芳香族ポリアミド短繊維集束体 |
| JP2012193480A (ja) * | 2011-03-17 | 2012-10-11 | Teijin Techno Products Ltd | 樹脂補強用短繊維束 |
| CN102797089A (zh) * | 2012-09-14 | 2012-11-28 | 山东爱地高分子材料有限公司 | 单丝状超高分子量聚乙烯纤维及其连续制备方法 |
| CN105164337B (zh) * | 2013-05-03 | 2018-03-02 | 帝人芳纶有限公司 | 制备对位芳族聚酰胺浆料和短切纤维的混合物的方法、混合物及其用途 |
| NL2014986B1 (en) | 2015-06-18 | 2017-01-23 | Filigrade B V | Waste separation method. |
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