CN115666927A - 聚合物泡沫层压结构 - Google Patents
聚合物泡沫层压结构 Download PDFInfo
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- CN115666927A CN115666927A CN202180036017.0A CN202180036017A CN115666927A CN 115666927 A CN115666927 A CN 115666927A CN 202180036017 A CN202180036017 A CN 202180036017A CN 115666927 A CN115666927 A CN 115666927A
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- Prior art keywords
- layer
- polymer foam
- laminate structure
- polymer
- solid
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Abstract
本发明涉及聚合物泡沫层压结构(1),包含‑密度大于1000g/l的第一固体层(101),其被至少一个第一功能层(103)覆盖,‑设置在至少一个第一功能层(103)上的聚合物泡沫层(105),‑密度大于1000g/l的第二固体层(109),其被至少一个第二功能层(107)覆盖,至少一个第二功能层(107)与聚合物泡沫层(105)相接触,其中聚合物泡沫层(105)的密度为20g/l至小于1000g/l。本发明还涉及制备聚合物泡沫层压结构(1)的方法以及包含聚合物泡沫层压结构(1)的复合部件(1000)。
Description
本发明涉及一种聚合物泡沫层压结构及其制备方法。本发明还涉及此聚合物泡沫层压结构以及包含本发明的聚合物泡沫层压结构的复合部件的用途。
如今,对建筑材料的要求,例如航空工业、汽车工业和海军工业都指向具有低重量,同时确保刚度、稳定性和强度的材料。特别地,在吸能材料的应用中,高密度的热塑性泡沫材料可以表现出高吸能性能,确保动态碰撞测试。
通常,这类泡沫的用途是在现有技术中已知的。例如DE 10 2018 111 510 A1,其中公开了一种吸能装置,其包括填充了第一类颗粒和第二类颗粒的管状元件,其中第一类颗粒相对于第二类颗粒是可变形的。对于第一类颗粒,可以使用类似泡沫的材料如聚苯乙烯,而较硬的第二类颗粒可以由聚氯乙烯制成。吸能过程在管状容器中进行。
另一项现有技术,EP 3 272 798 A1,涉及聚酰胺泡沫模制品及其制备方法。这类制品被描述为用于绝缘材料和汽车组件,例如引擎或气缸盖罩、车体结构和电气设备箱。
US 5746537描述了用作车内碰撞吸收元件的聚合物闭孔泡沫。所述热塑性泡沫例如PVC、PU和PS。未描述对金属表面的粘附性。
然而,当采用热塑性泡沫材料作为吸能部件时,现有技术尚未提供将泡沫与已知结构材料(如钢或铝或增强塑料)结合的令人满意的解决方案。
因此,本发明的目标问题是提供一种克服现有技术的缺点的聚合物泡沫层压结构,并且特别是提供聚合物泡沫材料与固体建筑材料的充分结合。本发明的另一个任务是提供一种制备这类聚合物泡沫层压结构的方法。
根据本发明,上述问题的第一方面通过聚合物层压结构(1)解决,其包含:
-密度大于1000g/l的第一固体层(101),其被至少一个第一功能层(103)
覆盖,
-设置在所述至少一个第一功能层(103)上的聚合物泡沫层(105),
-密度大于1000g/l的第二固体层(109),其被至少一个第二功能层(107)覆盖,所述至少一个第二功能层(107)与聚合物泡沫层(103)相接触,
其中聚合物泡沫层(105)的密度为20g/l至小于1000g/l。
此外,在本发明的第二方面中,通过制备聚合物泡沫层压结构(1)的方法已经解决了上述任务,特别是制备根据权利要求1至12中任一项的聚合物泡沫层压结构(1)的方法,包括如下步骤
a1)提供第一固体层(101),
a2)提供第二固体层(101),
b1)在第一固体层(101)上提供至少一个第一功能层(103),
b2)在第二固体层(109)上提供至少一个第二功能层(107),
c)在至少一个第一功能层(103)上方和至少一个第二功能层(107)下方提供聚合物泡沫层(105),
从而得到预层压结构,
d)在高温下压制预层压结构,以及
e)获得聚合物泡沫层压结构(1)。
通过本发明,已知的刚性建筑材料(如钢或铝或增强塑料)可与聚合物泡沫层热粘接,从而形成新型建筑材料。本发明的聚合物泡沫层压结构可用作吸能组件,例如碰撞元件。
如果聚酰胺用作聚合物泡沫层(105),本发明的聚合物泡沫层压结构(1)可以承受在阴极浸渍涂覆期间的高温(例如190℃的固化烘箱)。另一方面,与至少一个第一功能层(103)连结的刚性层(例如第一固体层(101),例如类似金属)与刚性且坚韧的聚合物泡沫(即聚合物泡沫层(105))的组合,可以获得具有优异的碰撞吸收性能的夹层部件(即聚合物泡沫层压结构(1))。如下文的实施例所示,在碰撞或弯曲测试期间,夹层结构(即聚合物泡沫层压结构(1))不会发生分离或损坏。
下文将详细描述本发明。
如果在下文关于根据本发明的聚合物泡沫层压结构(1)的描述中提及了特征,则它们也涉及本文所述的本发明的方法。同样,在根据本发明的方法的描述中提及的特征也涉及本发明的聚合物泡沫层压结构(1)。
在第一方面,本发明涉及聚合物泡沫层压结构(1),包括
-密度大于1000g/l的第一固体层(101),其被至少一个第一功能层(103)
覆盖,
-设置在所述至少一个第一功能层(103)上的聚合物泡沫层(105),
-密度大于1000g/l的第二固体层(109),其被至少一个第二功能层(107)覆盖,所述至少一个第二功能层(107)与聚合物泡沫层(103)相接触,
其中聚合物泡沫层(105)的密度为20g/l至小于1000g/l。
本文所用的术语“固体层”在本发明的意义上应理解为该特定层是由基本上没有孔隙的固体材料制成的,这与含有显著孔隙的术语“聚合物泡沫层”形成对比。为了在这两个术语之间划清界限,使用了大于或小于1000g/l的密度。
聚合物泡沫层(105)的密度根据DIN EN ISO 845 -10:2009测定,第一和第二功能层(103、107)的密度根据DIN EN ISO 1183测定。
为了增强第一固体层(101)和聚合物泡沫层(105)之间的接合,至少有一个第一功能层(103)覆盖在第一固体层(101)上,其特别是作为粘合层的作用。相似地,第二固体层(109)被至少一个与聚合物泡沫层(103)相接的第二功能层(107)覆盖。
根据本发明,第一和第二功能层(103、107)是用于在第一第二固体层(101、109)与聚合物泡沫层(105)之间获得紧锁力连接的工具。
特别地,第一和第二功能层(103、107)包含一种未增强的聚合物,由于其化学结构(聚酰胺),所述未增强聚合物特别适合于在第一和第二固体层(101、109)的表面形成良好的接合。因为第一和第二功能层(103、107)是高弹性的,因此可以补偿聚合物泡沫层(105)和第一和第二固体层(101、109)之间成型或弯曲时的张力。此外,由第一和第二固体层(101、109)和聚合物泡沫层(105)的不同热膨胀系数产生的应力也可以被吸收。
本发明带来的有利的效果是,作为第一和第二固体层(101、109)的已知刚性建筑材料(例如钢、铝、增强塑料)可以与聚合物泡沫层(105)形成热粘接,从而形成新型建筑材料,即本发明的聚合物泡沫层压结构(1)。
另一个优势是轻质材料的用途,即可将金属并入车体中。金属(例如用作固体层(101、109))被第一和第二功能层(103、107)覆盖,然后用标准钢铁加工技术(如深拉伸成型)进行转变。用于聚合物泡沫层(105)的颗粒泡沫可以在具有热蒸汽的模具中直接在第一和第二功能层(103、107)上转变(一步完成预发泡颗粒的层压和熔合)。或者将聚合物泡沫层(105)的颗粒泡沫用加热层压在第一和第二功能层(103、107)上。
与US 5756537相比,本发明能够将刚性聚合物泡沫与金属车体结合,此外还可以承受在例如阴极浸渍涂覆期间的高温。
在本发明的聚合物泡沫层压结构(1)的特定的实施方案中,聚合物泡沫是由预发泡的热塑性颗粒用蒸汽、红外辐射或微波焊接而成。预发泡的热塑性颗粒包括热塑性聚氨酯(TPU)(特别是BASF SE的Infinergy 100HD)或聚酰胺(PA6、PA12、PA6.12、PA6.12、PA6/6.36、聚醚酰胺嵌段共聚物、PA66、PA6T/66、PA6I/6T、PA6T/6I、PA9T、TPU及其混合物(特别是共聚酰胺PA6/6.36“Flex F 38”和PA6/6.36和BASF的PA6,密度1060kg/m3至1090kg/m3,相对密度(RV)3.7至3.9,熔点199℃))
在本发明的聚合物泡沫层压结构(1)的进一步开发中,第一和第二功能层(103、107)是包含聚酰胺、热塑性聚氨酯、热熔胶或其组合的热塑性层。
第一和第二功能层(103、107)优选为热塑性的,并且与第一和第二固体层(101、109)的表面相容。它们具有小于250℃的熔点或软化点。使用的材料优选聚酰胺(特别是PA6、PA6/6.36、PA6/66、PA12、PA6.12、PA6.10、PA6I/6T、己内酰胺或十二烷内酰胺共聚物)、热塑性聚氨酯(TPU)和热熔胶以及聚醚酰胺嵌段共聚物。
此处使用的“热熔胶”一词应理解为指在室温下或多或少为固体的无溶剂或无水产品,这些产品在热状态下以粘性液体的形式存在,并用于粘合表面。冷却状态下,它们会发生可逆地凝固并产生牢固地粘结。这类胶粘剂是基于不同化学原材料的热塑性聚合物。用于这些物理固化热熔胶胶粘剂的主要聚合物为聚酰胺树脂、饱和聚酯、乙烯-乙酸乙烯酯(EVA)共聚物、聚烯烃、嵌段共聚物(苯乙烯-丁二烯-苯乙烯或苯乙烯-异戊二烯-苯乙烯)和聚酰亚胺。聚酰胺、聚酯和聚酰亚胺用于所谓的高性能热熔胶粘剂,而乙烯-乙酸乙烯酯共聚物和聚烯烃用于所谓的熔体胶粘剂。
第一和第二功能层(103、107)还可包含其他功能性添加剂,例如增塑剂或功能性聚合物,例如马来酸酐接枝聚乙烯-α-聚烯烃共聚物或马来酸酐接枝聚乙烯-丙烯酸酯共聚物。
根据本发明,使用上述添加剂增加功能层的韧性和弹性是有效的,以使其可以更好地在聚合物泡沫层压结构(1)中形成且不被破坏。
在本发明的进一步开发中,聚合物泡沫层(105)具有100℃至280℃的软化点。
术语“软化点”是指在半结晶聚合物的情况下,熔融温度Tm,其可根据DIN EN ISO11357-3:2014通过差示扫描量热仪(DSC)测定。
另一方面,术语“软化点”是指在无定形聚合物的情况下,玻璃化转变温度Tg,其可根据DIN EN ISO 11357-2:2014在20K/min的加热速率下通过差示扫描量热仪(DSC)测定。
优选地根据本发明,当聚合物泡沫层(105)可通过以下方法获得时
-熔合预发泡聚合物颗粒,或
-在发泡剂存在下通过狭缝模头(slot die)挤出热塑性聚合物,或
-在高压釜中用发泡剂负载高于软化温度的热塑性聚合物,随后膨胀并成型,
-使用泡沫注塑成型机,
-将预发泡聚合物颗粒用蒸汽在特殊模具中直接熔合到第一和第二功能层(103、107)上。
在一个特定实施方案中,聚合物泡沫层(105)的聚合物泡沫可以是开孔或闭孔泡沫。
当聚合物泡沫层(105)包含聚酰胺、热塑性聚氨酯、聚醚酰胺嵌段共聚物、聚丙烯、聚苯乙烯、聚对苯二甲酸乙二醇酯(PET)、聚对苯二甲酸丁二醇酯(PBT)、聚酯/聚乳酸(PLA)、聚醚砜(PESU)及其混合物时,本发明的聚合物泡沫层压结构(1)是优选的。
聚酰胺具有高刚性、韧性和热稳定性的优点。
此外,当至少一个第一功能层(103)和/或至少一个第二功能层(107)包含聚酰胺,特别是PA6、PA6/6.36、PA12、PA610、PA6/66、PA6.12、聚醚酰胺嵌段共聚物时,本发明的聚合物泡沫层压结构(1)是优选的。
聚酰胺对丙烯酸酯预涂底漆的(primered)金属表面显示出良好的粘合性能。
在本发明的聚合物泡沫层压结构(1)中,至少一个第一功能层(103)和/或至少一个第二功能层(107)还可包含乙烯和/或α-烯烃和/或丙烯酸酯和/或马来酸酐的均聚物或共聚物。
均聚物或共聚物作为第一和第二功能层(103、107)的抗冲改性剂,并增加断裂伸长率,以使得其上已经层压第一和第二功能层(103、107)的金属部件(即固体层(101、109))可以使用深拉伸成型技术进行转变而不会破坏第一和第二功能层(103、107)。
特别地,均聚物或共聚物可以与马来酸酐接枝。
与马来酸酐的接枝增加了均聚物或共聚物与聚酰胺的相容性。
为了确保本发明的聚合物泡沫层压结构(1)的充分接合,至少一个第一功能层(103)和/或至少一个第二功能层(107)的厚度为20μm至2000μm。
厚度可通过超声测厚仪(slide gauge ultrasonic)测定。
功能层必须具有一定的厚度以确保颗粒泡沫部分(即聚合物泡沫层(105))的不均匀表面上的空间被第一和第二功能层(103、107)的聚合物填充(通常为400μm至1000μm)。另一方面,如果聚合物泡沫层(105)的聚合物泡沫具有光滑表面(如口模挤出的泡沫),则可以减小第一和第二功能层(103、107)的厚度。
第一和第二功能层(103、107)可以各自使用标准热塑性塑料生产工艺(铸造压延机)制备,然后将它们层压到第一和第二固体层(101、109)上,例如通过卷材涂装线或热压,通过间歇热压或双带压。
在本发明的第一个替代实施方案中,第一固体层(101)和/或第二固体层(109)是金属层,优选厚度为150μm至2000μm。这是典型厚度的金属卷材。
在本发明的第二个替代实施方案中,第一固体层(101)和/或第二固体层(109)是固体聚合物层,优选厚度为1mm至10mm。这是通过注塑成型可实现的典型的厚度。
根据本发明的聚合物泡沫层压结构(1)的第二个代替实施方案,作为第一固体层(101)和/或第二固体层(109)的固体聚合物层包括由碳纤维、玻璃纤维、芳纶纤维、玄武岩纤维、天然纤维、金属纤维、钛酸钾颗粒及其混合物增强的聚合物材料。
特别地,增强纤维可以作为粗纱或切割的连续纤维以通常的商用形式加入。此外,由织物、棉布、浮线、垫子、短纤维制成的上述增强材料也可以使用。
从机械稳定性的角度来看,当第一固体层(101)与至少一个第一功能层(103)紧锁力连接并且第二固体层(109)与至少第二功能层(107)紧锁力连接(force-lockingcontact)时,尤其优选本发明的聚合物泡沫层压结构(1)。
上述任务在本发明的第二方面通过制备聚合物泡沫层压结构(1)的方法实现,特别是如上所述的聚合物泡沫层压结构(1),包括以下步骤
a1)提供第一固体层(101),
a2)提供第二固体层(101),
b1)在第一固体层(101)上提供至少一个第一功能层(103),
b2)在第二固体层(109)上提供至少一个第二功能层(107),
c)在至少一个第一功能层(103)上方和至少一个第二功能层(107)下方提供聚合物泡沫层(105),
从而得到预层压结构,
d)在高温下压制预层压结构,以及
e)获得聚合物泡沫层压结构(1)。
根据本发明的发明方法主要具有与上述发明的聚合物泡沫层压结构(1)相同的优势效果。已知的刚性建筑材料作为第一和第二固体层(101、109)可与聚合物泡沫层(105)形成热粘接,以形成新型建筑材料。对于这种制造,可以使用通用的设备和适当的制备条件。
这种制备聚合物泡沫层压板结构(1)的方法可以在特定的实施方案中通过以下步骤进行更改
a1)提供第一固体层(101),
b1)在第一固体层(101)上提供至少一个第一功能层(103),
c1)提供用于聚合物泡沫层(105)的聚合物泡沫材料的预发泡热塑性珠粒,所述热塑性珠粒具有200g/l至400g/l的松散密度,
d1)通过用热蒸汽或热辐射(IR)将预发泡珠粒直接熔合到至少一个第一功能层(103)上,从而提供聚合物泡沫层(105),以及
e)获得聚合物泡沫层压结构(1)。
在涉及具体实施方案时,下文更详细地描述了本发明的方法。
本发明的另一方面涉及如上所述发明的聚合物泡沫层压结构(1)作为吸能装置的用途。
将通过根据本发明的实施例和对比实施例展示,所发明的聚合物泡沫层压结构(1)特别地适用于例如设置在碰撞元件中的吸能装置。
最后,本发明的一个具体的方面涉及复合部件(1000),包含
-根据本发明的且如上所述的聚合物泡沫层压结构(1),
-提供在聚合物泡沫层压结构(1)的第一固体层(101)或第二固体层
(109)上的至少一个聚合物层(1003),以及
-提供在至少一个聚合物层(1003)上并与根据权利要求1至12中任一项所述的聚合物泡沫层压结构(1)相对的金属层(1001),
其中至少一个聚合物层(1003)包含膨胀性材料。
换句话说,本发明的聚合物泡沫层压结构(1)增加了另一种功能,即防火和防热。
为了获得此额外的功能,金属层(1001)被设置成可以面对火源,例如火焰。优选的金属层(1001)的厚度为0.1mm至2mm。用作金属层的金属,可以使用钢、镀锌钢(热浸镀或电镀)、铝、锌、锡、铜、铬、镁或其合金。尤其适合的是熔点小于900℃的金属或合金,尤其是铝和锌。
特别地,金属层(1001)可以用基于聚丙烯酸酯或聚甲基丙烯酸酯、聚乙烯胺、磷酸、多聚磷酸;马来酸和丙烯酸和/或甲基丙烯酸和/或丙烯酸酯或甲基丙烯酸酯的共聚物,马来酸和苯乙烯的共聚物,乙烯和丙烯酸和/或甲基丙烯酸和/或丙烯酸酯或甲基丙烯酸酯和/或马来酸的共聚物和聚乙烯吡咯烷酮的粘合促进剂/底漆进行预处理,以确保与至少一个聚合物层(1003)的良好接合。粘合促进剂通常通过辊涂以水溶液的形式施加。
在金属层(1001)上设置至少一个聚合物层(1003),在本发明的意义上应理解为,这些层((1001)、(1003))优选地彼此完全且紧密地接触。
本发明的聚合物泡沫层压结构(1)的第一固体层(101)或第二固体层(109)设置在金属层(1001)对侧的至少一个聚合物层(1003)上。换句话说,金属层(1001)和第一固体层(101)或第二固体层(109)夹着至少一个聚合物层(1003)。
至少一个聚合物层(1003)包含作为其特定特征的膨胀性材料。
根据本发明,“膨胀性材料”一词涉及由于受热从而膨胀或变大的材料。这种膨胀使体积增加,密度减小。在本发明中,膨胀性材料用于吸收至少部分的热源的热量。
根据本发明的金属-聚合物层压材料(1)对位于后侧(即位于本发明的聚合物泡沫层压结构的一侧)的任意部件显示出良好的防火性能。
如本申请人的另一申请的实施例所示,当暴露在严重的高温/火焰的情况下,金属层(1001)可能会局部熔化或烧蚀,而包含在至少一个聚合物层(1003)中的膨胀性材料会开始膨胀并且会从金属层(1001)的缺口中挤出。当膨胀且挤出金属层(1001)时,膨胀材料对底衬层(105)起有效隔热的作用,从而保护本发明的聚合物泡沫层压结构(1)后侧的任意部件免受热源的高温。
膨胀效果源自膨胀性材料,例如膨胀石墨,其反复地发泡从表面进入损坏区域并更新被火焰损坏的膨胀材料层,例如膨胀石墨层。所发明的位于后侧的聚合物泡沫层压结构(1)首先具有结构功能。
为了提高金属层(1001)和至少一个聚合物层(1003)之间的接合,在金属层(1001)和聚合物层(1003)之间插入另一功能层,其特别地作为接合层。
进一步的目的、特征、优势和可能的应用源自以下对优选实施方案的描述,所述优选实施方案不通过图片限制本发明。任何描述的和/或图示的特征本身或以任何组合构成本发明的主题,甚至独立于它们在权利要求中的摘要或它们的追溯关系。如图,
图1示出了根据本发明的实施方案的聚合物泡沫层压结构1的示意图,
图2是关于聚合物泡沫层压结构1的实施例和对比实施例的图片,
图3是图2的实施例和对比实施例的力-位移曲线图,
图4是图2的实施例和对比实施例的吸能图,
图5a是试样“PA颗粒泡沫13”的力-位移曲线图,
图5b是在图5a图表下的试样图片,
图6a是试样“TPU泡沫”的力-位移曲线图,
图6b是在图6a图表下的试样图片,
图7是带有根据本发明的试样的测试装置的图片,
图8是对比弯曲功的图表。
在图1中给出了根据本发明实施方案的聚合物泡沫层压结构1的概览。示出了在顶部和底部的第一固体层101和第二固体层109。这两层分别朝向内部设置至少一个第一功能层103和至少一个第二功能层107。在其中间,设置聚合物泡沫层105。
实验
本发明的聚合物泡沫层压结构1的生产
将表1中列出的聚合物在ZE 25A UXTI双螺杆挤出机中按表1中所示的量混合,形成圆柱形颗粒。然后,使用压延挤出机将所得颗粒(PZ1和PZ2)挤出成膜。膜厚为400μm,宽为40cm。表1中给出的量的单位均为重量%。
P1:聚酰胺6(BASF SE的Ultramid B24N)
P2:PA6/6.36(BASF SE的Ultramid Flex F29)
Co1:低密度乙烯/丙烯酸正丁酯共聚物(Basell的Lucalen A2540 D)
Co2:乙烯丙烯共聚物,马来酸酐接枝(Exxon Chemicals的Exxelor 1801)
A1:N,N'-1,6-双[3,5-双-4-羟基苯基丙酰胺]己烷(BASF SE的Irganox B 11712x20KG 4G)
A2:滑石粉
表1:聚合物组成
表2:所用片材
然后将表2所述片材与预处理的金属条在热压机中合并形成层压板,作为第一和第二固体层101、109。金属条和片材被切割成如下尺寸:300mm×200mm。所用温度如图3所示。在80℃下整晚用干燥空气预干燥片材1和片材2。首先,制造棉条,将其与相应目标厚度的垫片一起放在冷压机中。压机以100kN的接触压力闭合并加热至表3中给出的目标温度。将温度保持60秒,然后将压机冷却至50℃并取出层压板。
如下金属条和聚合物条被用作第一和第二固体层101、109:
M1:用磷酸和丙烯酸水溶液经辊涂预处理的镀锌钢(Chemetal GmbH的GardobondX4543),金属片材厚度为250μm。
M2:用磷酸和丙烯酸水溶液经辊涂预处理的铝(Chemetal GmbH的GardobondX4595),金属片材厚度为300μm。
K1:聚酰胺PA6-GF35制成的注塑条(10mm×10mm×2mm)(BASF SE的UltramidB3EG7 sw 564)
特别地,第一和第二固体层101、109可以用基于聚丙烯酸酯或聚甲基丙烯酸酯、聚乙烯胺、磷酸、多聚磷酸;马来酸和丙烯酸和/或甲基丙烯酸和/或丙烯酸酯或甲基丙烯酸酯的共聚物,马来酸和苯乙烯的共聚物,乙烯和丙烯酸和/或甲基丙烯酸和/或丙烯酸酯或甲基丙烯酸酯和/或马来酸的共聚物和聚乙烯吡咯烷酮的粘合促进剂/底漆进行预处理,以确保与第一和第二功能层103、107的良好接合。粘合促进剂通常通过辊涂以水溶液的形式施加。
表3:制得的层压板
将表3所示的层压板压制入聚合物泡沫层压结构(PFLS)。使用下述表4中的聚合物泡沫层PSP1至PSP3作为核心层。将提供有功能层的一侧层压至所述聚合物泡沫层105的顶部和底部。
聚合物泡沫层可以使用专业人士已知的任何熔合方法制备。更准确的描述是使用基于蒸汽技术的自动成型设备生产。还有无水方法,例如Kurz公司的射频熔合法或FoxVelution公司的变温工艺也可以使用。
作为包含TPU的预发泡聚合物泡沫层,可使用BASF SE的Infinergy100HD。
如下所述制备包含PA的预发泡聚合物泡沫层。
熔融浸渍在一个由Leistritz公司的双螺杆挤出机组成的设备中进行,该挤出机分为八个长度相等的区域(Z1…Z8),螺杆直径为18mm,长径比为40,该设备还包含一个熔体泵,一个启动阀,一个熔体过滤器,一个多孔板和一个水下造粒机。
将聚酰胺与滑石粉在聚乙烯袋中混合,并通过加料装置在双螺杆挤出机中进料。聚酰胺在挤出机的1/3处熔化。在挤出机的大约1/3长度后,借助ISCO泵(Axel Semrau公司的柱塞泵)将推进剂泵入挤出机内。在挤出机的剩余部分中,通过双螺杆挤出机的温度控制来冷却聚合物熔体。当聚合物熔体通过多孔板时的温度应与区域8设定的温度相对应。通过熔体泵,将挤出机中的压力分布以一定的方式设定(压力-速度控制),使发泡剂完全混合到聚合物熔体中。除了设定双螺杆挤出机的压力分布外,熔体泵还可通过如下装置输送发泡剂和压制聚合物熔体(启动阀、熔体过滤器和多孔板)。将通过多孔板的熔体股在压力下引入水下制粒机,得到重量约3.5mg的膨胀聚胺颗粒。挤出机的总输出量保持恒定约4kg/h。水盒中的熔体股被附着在刀片环上的6片刀片切割。刀片环以约3500rpm的转速旋转,从而生产颗粒重量约3.5mg的膨胀颗粒,这些颗粒通过水回路从多孔板进到干燥器中,并被分离到收集容器中。
为了制备PSP1、PSP2和PSP3,使用如下组合物:
PSP1 | PSP2 | PSP4 | ||
聚酰胺(A) | ||||
聚酰胺6 | 50 | 50 | ||
聚酰胺6I/6T | ||||
聚酰胺(B) | ||||
共聚酰胺6/6.36 | 50 | 50 | 100 | |
成核剂 | ||||
滑石粉 | 0.5 | 0.5 | 0.5 | |
发泡剂 | ||||
氮气(N<sub>2</sub>) | 0.2 | 0.2 | 0.2 | |
二氧化碳(CO<sub>2</sub>) | 1.5 | 1.5 | 0.3 | |
水 | ||||
异戊烷 |
通过注入压缩空气将预膨胀的颗粒装入模具腔中(模具腔的尺寸:长300mm,宽200mm并且高25mm)。一定毫米的裂纹使用压制颗粒进行填充。将模具安装于成型机中。随后,通过将饱和蒸汽供给到模具腔中若干秒(交叉蒸汽加热),然后通过预膨胀颗粒的热熔合将饱和蒸汽供给到模具腔内若干秒(加压釜蒸汽加热)模制预膨胀颗粒。将冷却水注入模具腔中若干秒以冷却成型并焊接产品。颗粒泡沫成型的工艺条件和性能如表4所示。
PSP1:密度655g/l的PA泡沫,压制前厚度:10mm
PSP2:密度590g/l的PA泡沫,压制前厚度:25mm
PSP3:密度300g/l的TPU泡沫,压制前厚度:10mm
PSP4:密度230g/l的PA泡沫,压制前厚度:10mm
表4:所用的聚合物泡沫层
表5中所述的聚合物泡沫层压结构是通过将表5中所列的层置于压力为10kN的热压机中,并加热到表5中所示的层压温度而制成的。制得的聚合物泡沫层压板结构(PFLS)各自的总厚度如表5所示。
在PFLS2的情况下,可以观察到泡沫的轻微坍塌。
图2给出了所发明的聚合物泡沫层压结构1的实施例和对比实施例的图片。标注“5_2”的试样是夹在金属层(即金属片材)之间的PA颗粒泡沫,标注“13_1”的试样是用作聚合物泡沫层103的PA颗粒泡沫,而标注“Inf_3”的试样是夹在金属层(即金属片材)之间的TPU泡沫。
根据图2的实施例和对比实施例,力-位移曲线图如图3所示。可以发现试样5_2(PA颗粒泡沫+金属片材)具有很高的能量吸收和很高的刚性,而试样13_1(无金属片材,纯PA颗粒泡沫(PA颗粒泡沫5))只显示出较低的刚性和低能量吸收。另一方面,试样Inf_3(即(Infinergy+金属片材)具有很低的刚性但仍然有很高的弹性,并显示出良好的能量吸收。
图4展示了图2的实施例和对比实施例的吸能图像。由图3可知,试样13_1优于试样5_2。
图5a更详细地给出了试件5_2的力-位移曲线图,而图5b是该曲线图下的试样图片。这些曲线说明了不同但相似的试样在能量吸收方面的变化的方式。
在图6a中,更详细地展示了试样TPU泡沫的力-位移曲线图,而图6b是该曲线图下的试样图片。
在图7中,展示了一个测试装置,其对本发明的钢与聚酰胺的夹层试样进行了测试。与标准车体钢相比,本发明的试样具有最高的弯曲功,如图8所示。没有分层且泡沫核心几乎完好无损。
参考标注
1 聚合物泡沫层压结构
101 第一固体层
103 第一功能层
105 聚合物泡沫层
107 第二功能层
109 第二固体层
1001 金属层
1003 聚合物层
Claims (16)
1.聚合物泡沫层压结构(1),包含
-密度大于1000g/l的第一固体层(101),其被至少一个第一功能层
(103)覆盖,
-设置在至少一个第一功能层(103)上的聚合物泡沫层(105),
-密度大于1000g/l的第二固体层(109),其被至少一个第二功能层
(107)覆盖,所述至少一个第二功能层(107)与聚合物泡沫层(105)
相接触,
其中聚合物泡沫层(105)的密度为20g/l至小于1000g/l。
2.根据权利要求1所述的聚合物泡沫层压结构(1),其中聚合物泡沫层(105)具有100℃至280℃的软化点。
3.根据权利要求1或2所述的聚合物泡沫层压结构(1),其中聚合物泡沫层(105)通过以下方法获得
-熔合预发泡聚合物颗粒,或
-在发泡剂存在下通过狭缝模头挤出热塑性聚合物,或
-在高压釜中用发泡剂负载高于软化温度的热塑性聚合物,随后膨胀并成型,
-使用泡沫注塑成型机。
4.根据权利要求1至3中任一项所述的聚合物泡沫层压结构(1),其中聚合物泡沫层(105)包含聚酰胺、热塑性聚氨酯、聚醚酰胺嵌段共聚物、聚丙烯、聚苯乙烯、聚对苯二甲酸乙二醇酯、聚对苯二甲酸丁二醇酯、聚酯/聚乳酸、聚醚砜及其混合物。
5.根据权利要求1至4中任一项所述的聚合物泡沫层压结构(1),其中至少一个第一功能层(103)和/或至少一个第二功能层(107)包含聚酰胺,特别是PA6、PA6/6.36、PA12、PA610、PA6/66、PA6.12、聚醚酰胺嵌段共聚物。
6.根据权利要求1至5中任一项所述的聚合物泡沫层压结构(1),其中至少一个第一功能层(103)和/或至少一个第二功能层(107)还包含乙烯和/或α-烯烃和/或丙烯酸酯和/或马来酸酐的均聚物或共聚物。
7.根据权利要求6所述的聚合物泡沫层压结构(1),其中均聚物或共聚物为马来酸酐接枝的。
8.根据权利要求1至7中任一项所述的聚合物泡沫层压结构(1),其中至少一个第一功能层(103)和/或至少一个第二功能层(107)的厚度为20μm至2000μm。
9.根据权利要求1至8中任一项所述的聚合物泡沫层压结构(1),其中第一固体层(101)和/或第二固体层(109)为金属层,优选厚度为150μm至2000μm。
10.根据权利要求1至9中任一项所述的聚合物泡沫层压结构(1),其中第一固体层(101)和/或第二固体层(109)为固体聚合物层,优选厚度为1mm至10mm。
11.根据权利要求10所述的聚合物泡沫层压结构(1),其中作为第一固体层(101)和/或第二固体层(109)的固体聚合物层包括由碳纤维、玻璃纤维、芳纶纤维、玄武岩纤维、天然纤维、金属纤维、钛酸钾颗粒及其混合物增强的聚合物材料。
12.根据权利要求1至11中任一项所述的聚合物泡沫层压结构(1),其中第一固体层(101)与至少一个第一功能层(103)紧锁力连接,第二固体层(109)与至少一个第二功能层(107)紧锁力连接。
13.制备聚合物泡沫层压结构(1)的方法,特别是制备根据权利要求1至12中任一项所述聚合物泡沫层压结构(1)的方法,包括如下步骤
a1)提供第一固体层(101),
a2)提供第二固体层(109),
b1)在第一固体层(101)上提供至少一个第一功能层(103),
b2)在第二固体层(109)上提供至少一个第二功能层(107),
c)在至少一个第一功能层(103)上方和至少一个第二功能层(107)下方提供聚合物泡沫层(105),
从而得到预层压结构,
d)在高温下压制预层压结构,以及
e)获得聚合物泡沫层压结构(1)。
14.制备聚合物泡沫层压结构(1)的方法,特别是制备根据权利要求1至12中任一项所述聚合物泡沫层压结构(1)的方法,包括如下步骤
a1)提供第一固体层(101),
b1)在第一固体层(101)上提供至少一个第一功能层(103),
c1)提供用于聚合物泡沫层(105)的聚合物泡沫材料的预发泡热塑性珠粒,所述热塑性珠粒具有200g/l至400g/l的松散密度,
d1)通过用热蒸汽或热辐射将预发泡珠粒直接熔合到至少一个第一功能层(103)上,从而提供聚合物泡沫层(105),以及
e)获得聚合物泡沫层压结构(1)。
15.根据权利要求1至12中任一项所述的聚合物泡沫层压结构(1)作为吸能装置的用途。
16.复合部件(1000),包含
-根据权利要求1至12中任一项所述的聚合物泡沫层压结构(1),
-提供在聚合物泡沫层压结构(1)的第一固体层(101)或第二固体层
(109)上的至少一个聚合物层(1003),以及
-提供在至少一个聚合物层(1003)上并与根据权利要求1至12中任一项所述的聚合物泡沫层压结构(1)相对的金属层(1001),
其中至少一个聚合物层(1003)包含膨胀性材料。
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