CN1668444A - 玻璃纤维增强型热塑性塑料 - Google Patents
玻璃纤维增强型热塑性塑料 Download PDFInfo
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Abstract
本发明涉及通过直接与短玻璃纤维混合，获得长纤维增强型热塑性塑料(也称为热塑塑料)。
Description
技术领域
本发明涉及通过直接混合短玻璃纤维，来获得长纤维增强型热塑性塑料(也称为热塑塑料)。
本发明描述了玻璃和/或碳纤维增强的模制件的生产方法，其中平均纤维长度比使用常规混合的相同组成的热塑性模制组合物进行的传统注塑成型方法中获得的纤维长度要长得多。该方法的特征是首先产生一种聚合物熔体，在该聚合物熔体中混有常规的短纤维(短原丝，平均纤维长度小于10mm)，得到的熔体转移到注塑成型装置或压机上，通过注塑成型、压力成型或相当的方法形成所需的形状。关键是在纤维混入熔体后不再固化，不需要在成型之前再次熔化。该方法还可原则上转移到挤压法，例如型材挤塑和吹塑法。也可考虑用其它纤维材料作为增强材料，只要它们以切断成平均纤维长度小于25mm的形式进行称量。
背景技术
原则上，对于使用热塑性模制组合物生产纤维增强型模制件，使得平均纤维长度尽可能长是关注的，因为机械性能，尤其是刚度和强度是因此有利的。该方法应尽可能普遍的使用，同时也尽可能的少花费人力和原料成本。
为了生产长玻璃纤维增强的模制件，使用例如通过拉挤法(pultrusionprocess)形成的长纤维增强的颗粒或小球(通常长度为例如12-125mm)。该方法的缺点是在注塑成型机上加工该拉挤产品时，会在熔化过程中产生高机械应力，导致长纤维断裂。只有很少一部分长纤维保留。可通过和缓加工条件，例如使用具有低压缩的螺杆和高长度/直径比、低背压、尽可能低的注射速度和合适的单向阀来提高模制件中的平均纤维长度。还可通过与工具设计有关的方法来增加平均玻璃纤维长度，例如使用杆式浇注系统，避免在熔化通道中方向急剧改变。
为了部分解决在关键的熔化过程中玻璃纤维断裂的问题，开发了所谓的直接混合法，首先在双螺杆挤出机中熔化热塑性塑料。然后计量增强材料，并混合到熔化的塑料基质中。该方法可连续(在缓冲积蓄器的帮助下)或不连续进行。混合后，塑料/纤维混合物被转移到活塞式注射装置中，然后用注射活塞注射到成形池中。
在另一种已知方法中，首先将热塑性塑料熔化在双螺杆挤出机中，然后将熔体和增强纤维一起转移到第二个双螺杆装置中。在该装置中，混合两种组分。然后将该混合物以挤出物的形式排出，切到一定长度，用一输送系统运到压机中。US-A5 165 941描述了该方法的一个具体例子，其中使用至少25mm长的玻璃纤维来增强。
用长玻璃纤维增强模制件的已知生产方法具有在所有的情况下，必须使用长玻璃纤维的缺点，例如这些纤维在混合操作中需从粗纱上解绕下来。粗纱的处理比短玻璃纤维(纤维长度不超过6mm)的重力测量要复杂得多。
所有现有方法的基础在于，为了实现与常规注塑成型法相比长得多的玻璃长度，需要使用连续纤维(所谓的粗纱)，或与市售短玻璃纤维(长3-6mm的所谓短原丝)相比，长很多的玻璃纤维(在US-A 5 165 941所述的方法中需要至少25mm长的玻璃纤维)。
发明内容
然而现在已经惊奇的发现，即使使用较短的纤维(所谓的短原丝)，也可能通过使用合适的方法在模制中实现比用标准注塑成型法加工常规混合物能够实现的长得多的纤维长度。成功的唯一要求是将相应的玻璃纤维或碳纤维和缓的混入热塑性熔体，再和缓的加工熔体(优选立即加工)，尤其是模制组合物不固化和/或结晶。
特别优选的是在混合步骤中使用双柱挤出机(例如KWP生产的所谓的ZSK)或捏和机，注射装置是活塞型注塑成型机。
原则上，任何热塑塑料都适合本发明，只要它能够有利的使用玻璃或碳纤维增强或类似的增强材料。特别合适的是市售的热塑塑料，例如聚酰胺、聚亚烷基对苯二甲酸酯、不同的市售热塑塑料之间或者其与抗冲击改性剂的混合物。另外，该方法也适合高性能热塑塑料，例如聚苯硫。
热塑模制组合物可以含有常规使用的添加剂，例如加工辅助剂(润滑剂和模具释放剂)、弹性调节剂、耐火剂、成核剂(在半结晶聚合物的情况下)、着色剂、炭黑、导电性添加剂、防静电剂、增塑剂和其它填料、增强材料，尤其是矿物填料。
这些物质的添加，当然要以能够保持对根据本发明加入的纤维的损伤尽可能轻微为准。
应理解，本发明的纤维增强材料特别是玻璃纤维、碳纤维、钢纤维、镀金属玻璃纤维、天然纤维和聚合物纤维，条件是它们所用的形式是平均纤维长度优选为2-25mm，特别优选为3.5-6mm的纤维束，并且与所要用的模制组合物相容，并且在使用聚合物纤维时，不溶于模制组合物或在合适的加工温度下不熔化。
在最优选的方法的变化形式中，使用长3-6mm的短玻璃纤维，即所谓的短原丝。
特别优选的热塑塑料是聚酰胺-尤其是聚酰胺6和聚酰胺66、聚对苯二甲酸丁二酯及其与聚碳酸酯和/或橡胶的混合物。
已知许多制备聚酰胺的方法，这些方法中视所需的终产物而定，可以使用不同的单体结构装置、不同的链调节剂来实现所需的分子量，或者使用具有随后能够进行所需后处理的反应基团的其它单体。
聚酰胺制备的技术相关的方法优选通过缩聚作用在熔体中发生。在此，内酰胺的水解聚合也被理解为缩聚作用。
优选的聚酰胺是半结晶聚酰胺，可以从二胺和二羧酸和/或具有至少5个环上成员的内酰胺、或相应的氨基酸开始制备。
可考虑作为起始材料有脂族和/或芳族二羧酸，例如己二酸、2，2，4-和2，4，4-三甲基己二酸、壬二酸、癸二酸、异酞酸、对苯二酸；脂族和/或芳族二胺，例如己二胺、1，9-壬二胺、2，2，4-和2，4，4-三甲基己二胺、异构的二氨基-二环己基-甲烷、二氨基二环己基丙烷、二氨基甲基环己烷、苯二胺、二胺甲基苯；氨基羧酸，例如氨基己酸；或相应的内酰胺。也包括含有多种上述单体的共聚酰胺。
特别优选的是使用己内酰胺，最优选是ε-己内酰胺。
还特别合适的是基于PA6、PA66和其它脂族和/或芳族聚酰胺或共聚酰胺的化合物，其中化合物在聚合物链上每个聚酰胺基团上有3-11个亚甲基。
所使用的聚酰胺还可与其它聚酰胺和/或其它聚合物作为混合物使用。
聚酰胺模制组合物还可额外含有防火剂，例如多磷化合物、有机卤素化合物、含氮化合物/或氢氧化镁；稳定剂、加工辅助剂，例如润滑剂、成核剂；抗冲调节剂，例如橡胶或聚烯烃等。
具体实施方式
实施例1
本发明PA6GF30(含30wt％玻璃纤维增强的聚酰6)模制件的生产过程。为了制备本发明的模制组合物，称量PA6(DurethanB31 SK H2.0 900050；Bayer AG，Leverkusen，Germany的商品)，置于双螺杆挤出机的入口区，该挤出机与双活塞注射系统相连。用重力称量装置连续将短玻璃纤维CS 7928(Bayer AG，Leverkusen.Germany的商品)加入熔化的模制组合物中。混合后，将塑料/纤维混合物转移到活塞型注射装置中，用注射活塞注射到注塑成型工具(模制件重约700g；壁厚约3mm)中。双活塞注射系统确保双螺杆挤出机的连续操作。对于双活塞注射系统，在注射过程中混合的组合物被转移到非工作注射装置中。
实施例2(实施例1的比较实施例)
PA6GF30模制件用常规注塑成型材料的生产过程。为了相应模制件的生产，在标准注塑成型法的标准条件下，在实施例1所述的注塑成型工具的帮助下，在注塑成型机上对PA6GF30(DurethanBKV30 H2.0 900050；Bayer AG的商品)进行注射成型。
实施例3
本发明PA66GF30模制件的生产。为了制备本发明的模制组合物，称量热稳定性染成黑色的PA66(DurethanA 30 S H2.0 900050；Bayer AG的商品)，置于实施例1所述装置的入口区。用重力称量装置连续将短玻璃纤维CS 7928(BayerAG的商品)加入熔化的模制组合物中。混合后，将塑料/纤维混合物转移到活塞型注射装置中，然后在实施例1所述的注塑成型工具的帮助下进行注射成型。
实施例4(实施例3的第一个比较实施例)
PA6GF30模制件用常规注塑成型材料的生产过程。为了相应模制件的生产，在标准注塑成型法的标准条件下，在实施例1所述的注塑成型工具的帮助下，在注塑成型机上对PA6GF30(DurethanBKV30 H2.0 900050；Bayer AG的商品)进行注射成型。
实施例5(实施例3的第二个比较实施例)
不根据本发明，用连续玻璃纤维(具有11微米的纤维直径和适合聚酰胺的纤维尺寸)PA6GF30模制件的生产过程。为了制备该模制组合物，称量PA6(DurethanB31 SK H2.0 900050；Bayer AG的商品)，置于实施例1所述的双螺杆挤出机的入口区。通过双螺杆挤出机中螺杆的旋转运动，连续加入玻璃纤维。玻璃纤维混入已经熔化的模制组合物。玻璃纤维浓度可随着称量入的热塑塑料量、螺杆速度、纤维的所谓特数(tex number，是纤维丝中一束纤维中单根纤维的数目)或所用的所谓粗纱数目(纤维束的圈数)改变。
所需的连续纤维的计量比短玻璃纤维的计量要费事多得多，后者可以通过称重毫不困难的实现。在混合后，将塑料/纤维混合物转移到活塞型注射装置中，然后在实施例1所述的注塑成型工具的帮助下进行成型。
从模制件中除下边缘长度为55×55×3mm2的正方形平板和边缘长度为80×10×3mm2的扁平棒，测试其机械性质和玻璃纤维长度分布。结果如表1所示。
本发明实施例与比较实施例的比较显示，在双向穿透测试中强度、模量、弹性以及纤维长度都比比较测试的值高得多。
表1
| 实施例1 | 实施例2(实施例1的比较) | 实施例3 | 实施例4(实施例3的比较) | 实施例5(实施例3的比较) | |
| 3.5％外层纤维应变下的弯曲应力[Mpa] | 200 | 171 | 208 | 172 | 179 |
| 抗挠强度[Mpa] | 220 | 195 | 246 | 202 | 228 |
| 弯曲模量[Mpa] | 6590 | 5520 | 6320 | 5470 | 5910 |
| 玻璃纤维长度分布的平均值[微米] | 约420 | 约270 | 约490 | 约270 | 约830 |
该表格显示，在根据本发明生产的实施例1和实施例3的模制件中，弯曲应力、抗挠强度和弯曲模量这些重要的机械性质都有明显高得多的值。本发明的实施例3的玻璃纤维长度分布的平均值明显比在加工具有相同玻璃纤维浓度的已经制成的混合物时所能实现的平均值高得多(实施例4)。虽然用连续玻璃纤维制备的混合物的玻璃纤维长度(实施例5)比实施例3长，但是实施例3获得的更好的机械特性值。
Claims (10)
1.制备纤维增强型热塑模制组合物的模制件的方法，所述模制件具有至少400微米的平均长度，其特征在于，在混合装置中，将2-25mm长的纤维束均匀分布在热塑塑料熔体中，然后直接，即不经过中间冷却、固化和重熔，使熔体通过注塑成型或压力成型成形，并以该形状固化。
2.如权利要求1所述的方法，其特征在于，所述纤维束含有平均直径为9-17微米的具有一定尺寸的玻璃纤维。
3.如权利要求1所述的方法，其特征在于，所述纤维是平均直径为9-17微米的碳纤维。
4.如权利要求1所述的方法，其特征在于，所述热塑塑料熔体主要含有聚酰胺。
5.如权利要求1所述的方法，其特征在于，所述热塑塑料熔体主要含有聚酰胺6或聚酰胺66。
6.如权利要求1所述的方法，其特征在于，所述热塑塑料熔体主要含有热塑性聚酯。
7.如权利要求1所述的方法，其特征在于，所述热塑塑料熔体主要含有聚对苯二甲酸丁二酯。
8.如权利要求1所述的方法，其特征在于，所述热塑塑料熔体主要含有聚对苯二甲酸乙二酯。
9.如权利要求1所述的方法，其特征在于，所述热塑塑料熔体主要含有聚丙烯。
10.用任一上述权利要求所述方法获得的模制件。
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| DE10232485A DE10232485A1 (de) | 2002-07-19 | 2002-07-19 | Glasfaserverstärkte thermoplastische Kunststoffe |
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| CN1668444A true CN1668444A (zh) | 2005-09-14 |
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| EP (1) | EP1525082B1 (zh) |
| JP (1) | JP2005532934A (zh) |
| KR (1) | KR20050021509A (zh) |
| CN (1) | CN1668444A (zh) |
| AU (1) | AU2003246388A1 (zh) |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102516753A (zh) * | 2011-11-23 | 2012-06-27 | 安徽宜万丰电器有限公司 | 一种塑料连接器及其制造方法 |
| CN102679227A (zh) * | 2012-05-31 | 2012-09-19 | 东莞市帝信光电科技有限公司 | 一种塑胶散热式led灯泡及塑胶散热座 |
| CN104328517A (zh) * | 2014-11-17 | 2015-02-04 | 厦门厦迪亚斯环保过滤技术有限公司 | Pa6改性单丝的制造工艺 |
| CN105038178A (zh) * | 2015-07-24 | 2015-11-11 | 中广核俊尔新材料有限公司 | 玻纤增强聚碳酸酯复合材料及其制备方法和应用 |
| CN106661241A (zh) * | 2015-03-26 | 2017-05-10 | 住友理工株式会社 | 玻璃纤维强化热塑性树脂成型体和其制法 |
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| DE102005040620A1 (de) * | 2004-10-11 | 2006-04-13 | Bayer Materialscience Ag | Glasfaserverstärkte Polymer-Zusammensetzungen |
| US20080017655A1 (en) * | 2006-07-19 | 2008-01-24 | Martel Shelly A | Food container assembly |
| US20080063869A1 (en) * | 2006-08-23 | 2008-03-13 | Husky Injection Molding Systems Ltd. | Compounding molding system, amongst other things |
| CN104093541A (zh) * | 2012-01-26 | 2014-10-08 | 沃斯洛工厂有限公司 | 由纤维强化塑料制造用于固定轨道车辆的轨道的系统构件 |
| JP5738374B2 (ja) | 2013-09-27 | 2015-06-24 | 住友理工株式会社 | ガラス繊維強化熱可塑性樹脂成形体およびその製法 |
| CN107405801A (zh) * | 2014-12-10 | 2017-11-28 | 查尔斯斯塔克布料实验室公司 | 聚合物微小楔形物及其制造方法 |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3632254A (en) * | 1970-01-14 | 1972-01-04 | Dart Ind Inc | Apparatus for producing fiber reinforced plastics |
| US5165941A (en) * | 1989-09-05 | 1992-11-24 | Composite Products, Inc. | Extruder apparatus and process for compounding thermoplastic resin and fibres |
| US6186769B1 (en) * | 1999-04-06 | 2001-02-13 | Woodshed Technologies | Resin and fiber compounding apparatus for molding operations |
-
2002
- 2002-07-19 DE DE10232485A patent/DE10232485A1/de not_active Withdrawn
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- 2003-07-07 KR KR10-2005-7000907A patent/KR20050021509A/ko not_active Application Discontinuation
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102516753A (zh) * | 2011-11-23 | 2012-06-27 | 安徽宜万丰电器有限公司 | 一种塑料连接器及其制造方法 |
| CN102516753B (zh) * | 2011-11-23 | 2013-12-18 | 安徽宜万丰电器有限公司 | 一种塑料连接器及其制造方法 |
| CN102679227A (zh) * | 2012-05-31 | 2012-09-19 | 东莞市帝信光电科技有限公司 | 一种塑胶散热式led灯泡及塑胶散热座 |
| CN104328517A (zh) * | 2014-11-17 | 2015-02-04 | 厦门厦迪亚斯环保过滤技术有限公司 | Pa6改性单丝的制造工艺 |
| CN104328517B (zh) * | 2014-11-17 | 2017-04-26 | 厦门厦迪亚斯环保过滤技术有限公司 | Pa6改性单丝的制造工艺 |
| CN106661241A (zh) * | 2015-03-26 | 2017-05-10 | 住友理工株式会社 | 玻璃纤维强化热塑性树脂成型体和其制法 |
| CN106661241B (zh) * | 2015-03-26 | 2018-01-02 | 住友理工株式会社 | 玻璃纤维强化热塑性树脂成型体和其制法 |
| CN105038178A (zh) * | 2015-07-24 | 2015-11-11 | 中广核俊尔新材料有限公司 | 玻纤增强聚碳酸酯复合材料及其制备方法和应用 |
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| Publication number | Publication date |
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| JP2005532934A (ja) | 2005-11-04 |
| EP1525082B1 (de) | 2009-12-30 |
| AU2003246388A1 (en) | 2004-02-09 |
| DE50312291D1 (de) | 2010-02-11 |
| EP1525082A1 (de) | 2005-04-27 |
| WO2004009325A1 (de) | 2004-01-29 |
| DE10232485A1 (de) | 2004-01-29 |
| KR20050021509A (ko) | 2005-03-07 |
| US20040012121A1 (en) | 2004-01-22 |
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