CN107406614A - 使用微波热粘合制备基于热塑性弹性体的颗粒泡沫的方法 - Google Patents

使用微波热粘合制备基于热塑性弹性体的颗粒泡沫的方法 Download PDF

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CN107406614A
CN107406614A CN201680014626.5A CN201680014626A CN107406614A CN 107406614 A CN107406614 A CN 107406614A CN 201680014626 A CN201680014626 A CN 201680014626A CN 107406614 A CN107406614 A CN 107406614A
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F·普里索克
M·哈姆斯
M·舒埃特
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Abstract

本发明涉及一种由基于热塑性弹性体、特别是热塑性聚氨酯的泡沫颗粒制备颗粒泡沫的方法，其中泡沫颗粒用极性液润湿，并使用高频电磁辐射、特别是微波辐射在模具中粘合在一起。本发明还涉及由此获得的颗粒泡沫。

Description

使用微波热粘合制备基于热塑性弹性体的颗粒泡沫的方法
本发明涉及一种通过高频电磁辐射将泡沫珠粒热接合在一起来制备珠粒泡沫的方法。
诸如聚丙烯或聚苯乙烯珠粒泡沫的珠粒泡沫通常在自动模塑机中与过热水蒸汽熔合在一起，以形成例如用于包装工业的成型部件。TPU珠粒泡沫不仅可通过过热蒸汽熔合进一步加工，而且还可通过原位发泡或与反应性聚氨酯体系粘合来进一步加工。由于过热蒸汽熔合具有非常高的能量需求，因此寻求替代方案。原则上，借助热空气的熔合是可行的，但由于不理想的分布至今仍不能得到令人满意的部件，并且由于热空气的低的能量含量以及闭孔泡沫的差的热传导而需要长的循环时间。
在目前广泛应用的制造组成部件的方法中，预发泡的珠粒借助水蒸气热熔合在一起。将之前发泡的珠粒气动地(air-pneumatically)从料仓中抽吸入模塑机的压力填充装置中，用压缩空气压缩并吹入模具中。由于珠粒不含任何其他用于发泡的发泡剂，因此它们以压缩态(背压工艺)输送到模具中。在蒸汽压力为2.5至3.5巴下，使用水蒸汽作为传热介质将各珠粒熔合在一起。熔合后，将模制部件冷却，并使待脱模的模制部件的泡沫压力充分降低。用于例如EPP珠粒的方法的描述见于EP 0 588 321 A1中。
膨胀型热塑性聚氨酯(E-TPU)是最近出现的珠粒泡沫的成员，这在于E-TPU可以类似于上述方法熔合在一起，以形成高回弹性的组成部件，由于珠粒之间优异的粘着性，其可暴露于极端的动态应力下。基于热塑性弹性体的发泡材料及其制备方法例如由WO 2005/023920、WO 2007/082838、WO 2013/153190和WO 2014/198779已知。
WO 2007/023091记载了具有含水玻璃和绝热化合物(如石墨或炭黑)的聚合物涂层的聚苯乙烯泡沫珠粒，在不存在水蒸汽的情况下，将其进行压力烧结以形成成型泡沫制品。
将泡沫珠粒热粘合在一起的另一种方法是如尤其是WO 2001/64414中所述的高频熔合。在高频熔合中，待熔合在一起的发泡珠粒，特别是可膨胀的聚苯乙烯(EPS)、膨胀的聚丙烯(EPP)或可膨胀的聚对苯二甲酸乙二醇酯(EPET)被吸收电磁辐射的液体介质(例如水)围绕，然后通过施加电磁辐射(例如微波)的形式接合在一起。由于热塑性聚合物的较高的极性而导致吸水，因此，对于包含热塑性弹性体的泡沫珠粒而言，该方法仅是勉强可行的。此外，在大气压下在沸水上可达到的100℃温度通常不足以将弹性体珠粒熔合在一起。吸水使水充分渗入珠粒中，并且加热不仅在接触点处，而且在珠粒内也是有效的。结果是，珠粒可能在熔合之前破裂。
DE 10 2013 012 515 A1记载了一种通过具有改善的能量平衡的感应加热而将泡沫珠粒、特别是EPP或EPS接合在一起的方法。然而，通过感应加热来制备成型部件以部分珠粒上、至少在待接合在一起的表面处的一些导电性为先决条件。这可通过用导电填料例如金属粉末或炭黑、纳米管涂覆来实现。喷涂是涂覆珠粒的可能方法的一个实例。
本发明解决的问题是克服上述缺点，并提供一种通过高频电磁辐射、尤其是微波辐射将泡沫珠粒热接合在一起来制备珠粒泡沫的方法。
该问题通过一种由基于热塑性弹性体的泡沫珠粒来制备珠粒泡沫的方法解决，该方法包括用极性液体润湿泡沫珠粒，然后在模具中通过高频电磁辐射将其热接合在一起。
有用的热塑性弹性体包括，例如，热塑性聚氨酯(TPU)、热塑性聚酯弹性体(例如聚醚酯和聚酯酯)、热塑性共聚酰胺(例如聚醚共聚酰胺)或热塑性苯乙烯-丁二烯嵌段共聚物。特别优选基于热塑性聚氨酯(TPU)的泡沫珠粒。
泡沫珠粒可通过用悬浮液中的发泡剂浸渍热塑性弹性体丸粒，或者通过用发泡剂熔融浸渍熔融的热塑性弹性体并随后造粒而获得。用于制备基于热塑性弹性体的泡沫珠粒的合适的方法记载于例如WO 2005/023920、WO 2007/082838、WO 2013/153190和WO 2014/198779中。
制备泡沫珠粒所用的热塑性弹性体优选具有根据DIN 53505测定的肖氏(Shore)硬度在25A至82D的范围内，优选在30A至80D的范围内，且更优选在65A至96A的范围内。
所用的泡沫珠粒的堆积密度优选在30至250kg/m3的范围内。
甚至相对较小比例的用作微波吸收剂的极性液体通常对于通过高频电磁辐射的熔合是足够的。泡沫珠粒通常用0.1至10重量％、优选1至6重量％的比例的极性液体润湿，基于所使用的泡沫珠粒计。
极性液体可使用常规的涂覆技术(例如喷涂、浸渍或润湿)，在用和不用额外的辅助材料的情况下而施用到泡沫珠粒上。为此，可以采用常规的混合器、喷涂装置、浸渍装置和/或滚筒装置。
特别优选用电偶极矩为5至15×10-30Cm的极性液体润湿泡沫珠粒。极性液体的沸点优选为120至350℃，优选为200至300℃。当极性液体的沸点高于热塑性的泡沫珠粒的熔点时，热接合在一起可在大气压力下进行，与水蒸汽不同。
合适的极性液体的实例是包含极性基团的微波吸收烃。可能的极性基团包括酯、胺或其他带杂原子的基团。优选用作极性液体的为羧酸和二醇或三醇的酯，例如乙酸或柠檬酸的乙二醇酯、乙酸或柠檬酸的甘油酯或二醇和液体聚乙二醇如三乙二醇或三丙二醇。
特别优选泡沫珠粒用三乙酸1,2,3-丙三醇酯(三醋精，三乙酸甘油酯)、三乙二醇或三丙二醇润湿。
泡沫珠粒也可具有功能性涂层，例如耐磨或低熔点聚氨酯涂层。此处，涂层中有用的其他添加剂包括能够吸收热和/或IR辐射的物质例如亚硝酸硼和氧化铝，或导电碳例如石墨，通过所述方法其能够在E-TPU组成部件内产生封闭网络。也可以在涂层中用非常少量的颜料进行着色，而不必对泡沫珠粒进行大量着色。
还可以在熔合之前将各种纤维(塑料、玻璃、金属)施加到泡沫珠粒的表面，以在加工后在组成部件内形成它们自己的网络。这可提供改进的机械性能。
令人惊讶地发现，本发明的方法由足够的微波吸收和低能量输入提供泡沫珠粒的精确的热接合(熔合)。
泡沫珠粒的热接合通过高频电磁辐射、尤其是通过微波在模具中进行。高频应理解为指频率不低于100MHz的电磁辐射。所用的电磁辐射的频率范围通常为100MHz至300GHz。优选使用频率范围为0.5至100GHz、更优选为0.8至10GHz的微波，并且照射时间为0.1至15分钟。微波的频率范围优选与极性液体的吸收行为匹配，或者相反地，极性液体根据它的吸收行为相对于所用的微波器具的频率范围的强度来选择。
本发明的方法使得可以在非常宽的频率范围内将泡沫珠粒熔合在一起。即使在水不会引起共振的频率范围内，涂覆的泡沫珠粒也优先在接触面加热，因此在整个珠粒在内部加热太多并且塌陷之前，这些即熔合在一起。
本发明包括将泡沫珠粒首先用极性液体稀薄地润湿，放入不吸收微波的模具中，然后通过微波熔合在一起。
极性液体稀薄地铺展在E-TPU珠粒的表面，然后有效并均匀地快速粘附在其上。随后在微波中照射时，新鲜涂层几乎完全吸收了能量，因此珠粒表面以精确的方式加热，从而实现与相邻珠粒的非常好的交熔(intermelting)。随后，将极性液体溶入热塑性弹性珠粒如塑化剂中，并且在熔合后对珠粒泡沫的性质没有任何不利影响。
极性液体由于极性而容易被E-TPU吸收。在继续处理/加热E-TPU珠粒的过程中，增塑剂(与PS和PP珠粒不同)将渗透到E-TPU珠粒中，因此当它们热接合在一起以形成珠粒泡沫时，不会破坏各泡沫珠粒之间的粘结。
本发明还提供可通过上述本发明方法获得的珠粒泡沫。它们的DIN 53504断裂伸长率优选为50至800％，且更优选为100至300％。根据DIN EN ISO 1183-1A测定的泡沫片材的密度通常在100至400g/L的范围内。
在需要特别有弹性而又轻质的结构材料的所有市场中，例如在保护性包装，即高敏感商品的智能包装中，可以想到应用本发明的珠粒泡沫。然而，它们也可用于运动地板，以及汽车结构或机械工程中的应用。
由于它们的弹性性质，本发明的珠粒泡沫可用于运动、鞋类和包装领域中的应用，例如作为安全鞋或用于电子元件或器具的包装。
实施例
所用的材料：
E-TPU Infinergy 32-100U10，基于热塑性聚氨酯的膨胀型基本上闭孔的泡沫珠粒，通过购自BASF Polyurethanes GmbH的粒化的在压力和高温下的膨胀获得，堆积密度为110g/L和150g/L。
极性液体：三乙酸甘油酯(三醋精，三乙酸1,2,3-丙三醇酯)
三乙二醇
三丙二醇
乙酰柠檬酸三丁酯
粘合剂：购自BASF Polyurethanes GmbH的Elastopave 6550/101，密实的2-组分聚氨酯体系
设备：
MLS-Ethos plus实验室微波系统，最大输出功率为2.5kW。
测量方法：
堆积密度通过用膨胀的珠粒填充200ml容器并通过称量确定重量来测定。此处，可假定±5g/L的精确度。
泡沫片材的密度根据DIN EN ISO 1183-1A测定。
泡沫片材的压缩强度根据DIN EN ISO 3386在10％、25％、50％和75％压缩下测定。
在根据ASTM D395处理(6h/50℃/50％)后，测定泡沫片材(鞋泡沫)的压缩形变。
泡沫片材的回弹性根据DIN 53512测定。
断裂伸长率和拉伸强度根据DIN 53504测定。
实施例B1：
将45重量份的堆积密度为110g/L的E-TPU泡沫珠粒与2.4重量份的三乙酸甘油酯一起置入容器中。摇动容器以使E-TPU泡沫珠粒在60秒的时间内被三乙酸甘油酯完全润湿。
将47.4克经湿润但仍松散的各珠粒填充到200mm×200mm×10mm的可用于微波炉加热的模具中。高度可调的盖子对珠粒施加轻微的压力。将该填充的模具以30°角倾斜放置在实验室微波炉转盘的外边缘上，并在400瓦特下照射40秒，将模具绕其垂直轴旋转180°，并在400W下再照射40秒，然后将该模具绕其垂直轴再旋转90°，然后在400W下再水平照射40秒。将模具从微波炉中取出并在水浴中冷却至室温。然后可移出熔合在一起的泡沫片材。
实施例B2：
将55重量份的堆积密度为130g/L的E-TPU泡沫珠粒与2.8重量份的三乙酸甘油酯一起置入容器中。摇动容器以使E-TPU泡沫珠粒在60秒的时间内被三乙酸甘油酯完全润湿。
将57.8克经湿润但仍松散的各珠粒填充到200mm×200mm×10mm的可用于微波炉加热的模具中。高度可调的盖子对珠粒施加轻微的压力。将该填充的模具以30°角倾斜放置在实验室微波炉转盘的外边缘上，并在400瓦特下照射45秒，将模具绕其垂直轴旋转180°，并在400W下再照射45秒，然后将该模具绕其垂直轴再旋转90°，然后在400W下再水平照射45秒。将模具从微波炉中取出并在水浴中冷却至室温。然后可移出熔合在一起的泡沫片材。
实施例B3：
将55重量份的堆积密度为130g/L的E-TPU泡沫珠粒与2.8重量份的三乙二醇一起置入容器中。摇动容器以使E-TPU泡沫珠粒在60秒的时间内被三乙二醇完全润湿。
将57.8克经湿润但仍松散的各珠粒填充到200mm×200mm×10mm的可用于微波炉加热的模具中。高度可调的盖子对珠粒施加轻微的压力。将该填充的模具以30°角倾斜放置在实验室微波炉转盘的外边缘上，并在400瓦特下照射40秒，将模具绕其垂直轴旋转180°，并在400W下再照射40秒，然后将该模具绕其垂直轴再旋转90°，然后在400W下再水平照射40秒。将模具从微波炉中取出并在水浴中冷却至室温。然后可移出熔合在一起的泡沫片材。
实施例B4：
将55重量份的堆积密度为130g/L的E-TPU泡沫珠粒与2.8重量份的乙酰柠檬酸三丁酯一起置入容器中。摇动容器以使E-TPU泡沫珠粒在60秒的时间内被乙酰柠檬酸三丁酯完全润湿。
将57.8克经湿润但仍松散的各珠粒填充到200mm×200mm×10mm的可用于微波炉加热的模具中。高度可调的盖子对珠粒施加轻微的压力。将该填充的模具以30°角倾斜放置在实验室微波炉转盘的外边缘上，并在400瓦特下照射45秒，将模具绕其垂直轴旋转180°，并在400W下再照射45秒，然后将该模具绕其垂直轴再旋转90°，然后在400W下再水平照射45秒。将模具从微波炉中取出并在水浴中冷却至室温。然后可移出熔合在一起的泡沫片材。
对比试验V1：
使用水蒸气将60g密度为110g/L的未涂布的E-TPU泡沫珠粒熔合在一起，以形成成型的泡沫制品。
对比试验V2：
使用9重量％的粘合剂将60g密度为110g/L的未涂布的E-TPU泡沫珠粒熔合在一起，以形成成型的泡沫制品。
对比试验V3：
使用23重量％的粘合剂将60g密度为110g/L的未涂布的E-TPU泡沫珠粒熔合在一起，以形成成型的泡沫制品。
将来自实施例B1-B4和对比试验V1-V3的泡沫片材的性能总结在表1中。
来自实施例B1-B4的泡沫片材相对于来自对比试验V2和V3的粘着的泡沫片材表现出较高的回弹性。
还有利的是，微波熔合(实施例B1)可产生比通过水蒸汽熔合(对比试验V1)的更低的组成部件重量。回弹性的增加和密度的降低被认为是有利的。
另外特别的优点是，相对于与水蒸汽(对比试验V1)和粘着的泡沫片材(V2和V3)以标准方式熔合在一起的泡沫片材，实施例B2和B3的泡沫片材具有高的断裂伸长率。
特别地，为了获得具有良好的机械性能的轻质组成部件，低密度、高拉伸强度和断裂伸长率以及高回弹性的组合是令人满意的。

Claims (10)

1.一种由基于热塑性弹性体的泡沫珠粒制备珠粒泡沫的方法，其包括用极性液体润湿泡沫珠粒，并通过高频电磁辐射将其在模具中热接合在一起。
2.根据权利要求1所述的方法，其中泡沫珠粒通过频率范围为100MHz至300GHz的微波热接合在一起。
3.根据权利要求1或2所述的方法，其中使用热塑性聚氨酯的泡沫珠粒。
4.根据权利要求1至3中任一项所述的方法，其中使用堆积密度在30至250kg/m3范围内的泡沫珠粒。
5.根据权利要求1至4中任一项所述的方法，其中极性液体以0.1至10重量％的比例润湿，基于泡沫珠粒计。
6.根据权利要求1至5中任一项所述的方法，其中极性液体的沸点在120℃至250℃的范围内。
7.根据权利要求1至6中任一项所述的方法，其中使用的极性液体包括(a)羧酸和二醇或三醇的酯或(b)乙二醇或液体聚乙二醇或(a)和(b)的混合物。
8.根据权利要求1至5中任一项所述的方法，其中使用的极性液体包括乙酸或柠檬酸的乙二醇酯、乙酸或柠檬酸的甘油酯、三乙二醇、三丙二醇或其混合物。
9.一种可通过权利要求1至8所述的方法获得的珠粒泡沫。
10.将根据权利要求9所述的珠粒泡沫用于包装或鞋类的方法。
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KR102449529B1 (ko) 2022-09-29
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US20180251621A1 (en) 2018-09-06
RU2017136175A (ru) 2019-04-15
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