CN1054799C - 纤维增强聚合物材料的制造方法和用于该方法的挤出机 - Google Patents

纤维增强聚合物材料的制造方法和用于该方法的挤出机 Download PDF

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CN1054799C
CN1054799C CN95192137A CN95192137A CN1054799C CN 1054799 C CN1054799 C CN 1054799C CN 95192137 A CN95192137 A CN 95192137A CN 95192137 A CN95192137 A CN 95192137A CN 1054799 C CN1054799 C CN 1054799C
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M·A·夫拉格
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Abstract

纤维增强的聚合物材料的制造方法，包括纤维束在弧形支持表面(2)上按弧形线的方向滑过，和通过该表面上的多个槽缝(4)向纤维束注射熔化的或液体的聚合物，每一槽缝与纤维束保持横向。该方法能够以高生产速度和低成本有效浸渍材料。

Description

纤维增强聚合物材料的制造方法和用于该方法的挤出机
本发明涉及熔体浸渍方法，尤其用于制备纤维增强的树脂材料。
纤维增强树脂材料有很高的强度，但质地轻，因而在无数工业领域中是非常理想的建筑用材。
制造此类材料的方法描述在EP-B-0167303中，其中纤维束在有弧形表面的加热挤出机机头上滑过，在构成纤维束的单丝纤维的排列方向的横向，从弧形表面上的槽缝，将熔化的热塑性聚合物注射入纤维束。
当对于较高粘性的材料使用这一方法时，会经历棘手的实际操作问题：挤出的聚合物趋向于将纤维束从挤出机机头的表面推开，而不是渗透入纤维束，从而涂覆纤维束的各纤维。没有被聚合物包围(润湿)的纤维不会对复合材料的机械强度有益处。在另外的加工步骤中，能够改进纤维的润湿状况，但这通常会导致纤维长度下降，因而降低纤维的增强效率。通过提高纤维在挤出机机头上的压力来克服这一问题的尝试导致在挤出机机头上有不可接受的高磨擦作用。
EP-A-397506公开了一种不同于EP-B-167303的方法，在弧形表面的反侧有两个狭缝状进料口，或两个以上的这样的进料口。EP-A-397506没有公开具有一个以上狭缝状开口的任何技术效果。
本发明提供一种纤维增强的聚合物材料的制造方法，包括以下步骤：纤维束在弧形支持表面上按弧形线的方向滑过，和向纤维束注射熔化的或液体的聚合物，其特征在于聚合物通过该表面上的至少8个槽缝被注射，每一槽缝基本上与纤维束保持横向。
本发明的方法使材料获得惊人的高效的浸渍效果；例如，它确保纤维束中各纤维被聚合物包围。因而能够生产出比现有技术更均匀的材料。
还有，该方法能够用来以较高的生产速度和低的成本制造纤维增强的聚合物树脂材料。
下面更详细地描述本发明的方法；纤维束在弧形表面上滑过。使用弧形表面能使纤维中的轴向张力转变成一种纤维作用于支持表面的径向力。这一径向力会受到纤维中的轴向预张力、纤维在该表面上的接触角和该表面的半径的影响。在这些参数当中，表面几何形状能够在一定的拉挤成型速度、纤维渗透性和聚合物粘度方面被最优化。
例如，当支持体是圆柱体时，可由支持体表面提供弧形支持。此外，它还能够通过切削出贯穿支持体的弧形截面或沟槽来提供。支持体的剩余部分可以是适合与其它设备一起操作的(与该设备一起使用的)任何的形状。例如，它可以被安装在挤出机上。优选的是，侧壁从该表面向上延伸，以便有利于控制纤维束通过它，并防止聚合物从纤维束下方侧漏。
熔化的或液体的聚合物，一般是热塑性聚合物(虽然能够使用热固性树脂)，受压力作用通过浸渍模具的弧形表面的多个槽缝。这些槽缝基本上与纤维排列方向和纤维束运动方向保持横向，因为，要不然纤维会被夹持在槽缝中。在弧形表面至少有8个槽缝，但优选有更多个，例如至少12个。槽缝的数目取决于，例如，待浸渍的纤维束的厚度，所使用的聚合物的粘度和所需要的拉挤成型速度。聚合物在模具表面和玻璃纤维之间产生膜。这一聚合物膜同时为本工艺方法起润滑作用并浸渍玻璃纤维。由于纤维是从一端浸渍，空气通过纤维束的另一端排出，减少了复合材料的孔隙度。聚合物膜的厚度是重要的参数。如果膜太薄，那么纤维将会接触模具表面，在模具表面和纤维之间产生摩擦力，不再进行纤维的浸渍。如果膜太厚，聚合物将会推开纤维和流过(而不是通过)纤维束，在复合材料中产生大量的孔隙。一般的膜厚是在0.05-1mm范围内。
当纤维在模具表面的槽缝上方通过时，一定量的聚合物通过槽缝释放出来形成某一厚度的膜。这种膜的厚度如以上所解释的那样加以限定，而在高粘度聚合物的情况下，当根据现有技术的方法进行操作时没有足够的聚合物来浸润纤维束中所有的单丝纤维。在模具表面之后，聚合物被压缩入纤维束，提高浸渍程度和减少聚合物膜的厚度。在膜厚快要减少至0和纤维接触模具表面之前，通过模具的另一槽缝将聚合物加入到膜中，一直到纤维束被完全浸渍。对于较低粘度的聚合物，50Pa.s和50Pa.s以下(在103-104Pa.s剪切应力和操作温度下)，聚合物通过纤维束的移动速度是如此的高，以致于一个槽缝和模具上的很小的接触区域就足够了。但对于较高粘度的聚合物来说，100Pa.s和100Pa.s以上(在103-104Pa.s剪切应力和操作温度下)，拉挤成型速度需要降低到这样一种程度：该方法不再在经济上有吸引力。本发明的方法特别适合于具有低于50(根据相应的ASTM方法)的相对粘度的热塑性聚合物。
槽缝之间的距离不必相等。初始浸渍比在本方法快要结束时的浸渍要快得多。纤维首先到达的槽缝应该较窄，逐渐在两槽缝之间增大间隔。
浸渍程度也取决于弧形表面积与槽缝面积之比。这种比值一般是在5-20范围内。在纤维束的横向上每一槽缝的长度是根据纤维束经过弧形表面的宽度来选择的；很显然，仅仅浸渍纤维束的一部分(例如中间)是不令人满意的。
沿纤维束方向每一槽缝的宽度主要取决于聚合物的粘度。例如，槽缝不应造得太狭窄，以致于引起槽缝堵塞；然后，同时窄的槽缝使某些聚合物(如聚丙烯)剪切稀化。一般来说，多而窄的槽缝优越于少而宽的槽缝。对于高粘度的聚合物，槽缝的典型宽度是在0.2-1.5mm范围内，优选在0.2-0.5mm范围内。
槽缝一般通过例如挤出机进给聚合物，如果使用热塑性聚合物的话，挤出机可以加热。挤出机与多个槽缝通过(例如)支持体上的孔来连通。
通过弧形表面的槽缝供给聚合物，在所要浸渍的纤维束下方产生聚合物膜，它在整个接触表面上延伸。这一膜实际上消除了在纤维束和弧形表面之间的摩擦力。所以，在纤维束内没有积累张力，张力一般引起纤维损坏和限制本方法的生产速度。
通过将纤维束铺展在弧形表面上来改进浸渍程度，从而减少该表面上纤维束的厚度。纤维束的厚度的减少会减少聚合物移动通过的长度，即浸渍路径。优选的纤维束厚度是在5-25根单丝纤维的范围内。
适合用于本发明的方法中的装置能够适当地设计小一些，以用于串联的浸渍方法，如型材(profile)的拉挤成型或绕丝。
合适的增强纤维的例子是玻璃纤维，碳纤维和芳酰胺纤维。合适的热塑性聚合物(用它浸渍这些纤维)的例子，包括聚烯烃，如聚乙烯和聚丙烯，聚酯如聚对苯二甲酸乙二醇酯(PET)和聚酮类。也可以使用热固性聚合物，如酚醛树脂和环氧树脂。
下面参考附图，通过实施例更详细地说明本发明，其中：
图1是适合用于本发明的方法的装置的一部分的透视图，和
图2是所使用的图1的装置(纤维束通过它的表面)的部分横截面图。
参见图1，支持体1具有带侧壁3的(即支持体中沟槽形式的)弧形表面2。在弧形表面提供至少8个槽缝4，通过槽缝聚合物被注射入纤维束。支持体一般连接于挤出机(未画)，挤出机为支持体中的中心孔5提供聚合物，该孔与槽缝4连通。
参见图2，纤维束6在方向7上经过弧形表面2。聚合物通过通路8注射入纤维束，接着通过连接于挤出机的中心孔5提供聚合物。从通路8出来的聚合物趋向于在纤维束6和弧形表面2之间的接触区域产生聚合物膜9，这用来减少它们之间的磨擦。
下面的实施例用来说明本发明。
实施例
根据本发明的方法，2400tex玻璃纤维(有合适的施胶剂)用聚丙烯母体浸渍。聚丙烯的熔体流动指数(MFI)为25gr/10min和相对粘度为2.1(根据ASTM D 1601-86，在浓度0.3％的十氢化萘溶液中，)。如图1所示，在挤出机模头上拔出玻璃纤维。在纤维方向的横向，弧形表面的宽度是14mm。纤维束在该表面的整个宽度上被铺展开，将纤维束的厚度减少至约7根单丝纤维。弧形表面的半径是25mm和纤维在该表面上的接触角是100°。在该表面有11个槽缝，沿着纤维方向在它们之间逐渐增大间隔；每一槽缝的宽度是0.35mm。纤维束中轴向张力是约80N。挤出机模头安装在挤出机上，它将聚丙烯加热至250℃和将聚丙烯以2巴的压力供给该模具。浸渍纤维然后被导引通过升温的圆口模头产生线料，线料能够被短切成粒料用于注射模塑。拉挤成型速度是20m/min。
由粒料注塑获得试验样品并测量它们的拉伸和挠曲性能。所测得的拉伸强度是105MPa，挠曲强度是195MPa，和挠曲模量是9.3GPa。
对于本技术领域中的熟练人员来说，很显然，从上述描述和附图能够对本发明进行各种改进。这些改进希望落在所附的权利要求的范围内。

Claims (7)

1.纤维增强的聚合物材料的制造方法，包括以下步骤：纤维束(6)在有弧形支持表面(2)的挤出机模头上按弧形线的方向滑过，和向纤维束注射熔化的或液体的聚合物，其特征在于聚合物通过该弧形表面(2)上的至少八个槽缝(4)被注射，每一槽缝基本上与纤维束(6)保持横向。
2.根据权利要求1所要求的方法，其中在弧形支持表面(2)存在至少12个横向槽缝(4)。
3.根据权利要求1或2所要求的方法，其中在纤维束运动方向(7)上，逐渐在槽缝(4)之间增大间隔。
4.根据权利要求1所要求的方法，其中沿纤维束(6)的方向每一槽缝(4)的宽度是在0.2-1.5mm范围内。
5.根据权利要求1所要求的方法，其中聚合物的相对粘度是低于50。
6.根据权利要求1所要求的方法，其中聚合物是选自聚烯烃、聚酯和聚酮的热塑性聚合物。
7.适合用于权利要求1-6中任何一项的方法的挤出机模头，它包括中心孔(5)，通过径向通路(8)与弧形外表面上的槽缝(4)连通，特征在于有至少八个这样的槽缝。
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BR9507071A (pt) 1997-09-09
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