CN115943026A - 通过在升高的水温下进行水下造粒制备基于高温聚合物的粒料以制备（硬质）颗粒泡沫 - Google Patents

通过在升高的水温下进行水下造粒制备基于高温聚合物的粒料以制备（硬质）颗粒泡沫 Download PDF

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CN115943026A
CN115943026A CN202180050687.8A CN202180050687A CN115943026A CN 115943026 A CN115943026 A CN 115943026A CN 202180050687 A CN202180050687 A CN 202180050687A CN 115943026 A CN115943026 A CN 115943026A
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rigid
temperature
polymer
particulate foam
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C·特拉塞尔
M·涅裴特
F·霍普夫
D·侯雷因
M·冈劳弗
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Evonik Operations GmbH
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Abstract

本发明涉及使用水下造粒系统由包含至少一种聚合物的聚合物组合物制备(硬质)颗粒泡沫的方法，所述聚合物具有至少180℃的根据ISO 11357‑2(2014年7月出版)的玻璃化转变温度，其中将挤出机的聚合物熔体输送到加压的第一水回路中，其中压力在0.2至30巴范围内，和在所述水回路中的水温在105℃至180℃范围内，将其造粒，以及这些(硬质)颗粒泡沫的用途。

Description

通过在升高的水温下进行水下造粒制备基于高温聚合物的粒料以制备(硬质)颗粒泡沫
技术领域
本发明涉及使用水下造粒系统由聚合物组合物制备由至少一种聚合物构成的(硬质)颗粒泡沫的方法，所述聚合物具有至少180℃的根据ISO 11357-2的玻璃化转变温度。
背景技术
由于工程塑料的高加工温度，根据现有技术，它们只能通过线料造粒进行加工。由此获得的圆柱形粒料成型体具有锋利的边缘。在运输和进一步加工的过程中，这些锋利的边缘导致粉尘和细粒子的形成增加，这使得必须采取适当的职业安全措施。此外，粒料的品质还会降低，因为粒料表面可能会损坏，例如出现微裂纹。
这些问题通过WO2005/056653中描述的水下造粒在一定程度上得到解决。然而，得自该方法的粒料具有增加比例的表面缺陷(凹痕)，并且有时甚至具有粒料内部的缺陷(空泡)。
为了去除劣质的粒料，需要费力的下游分选工艺。EP3377288和EP2361174描述了在工艺室中通过水下造粒制备塑料粒料的方法，在所述工艺室中工艺流体在至少2.0巴的工艺压力下具有高于120℃的温度。然而，所述塑料粒料的品质不足以满足许多应用的要求。
原则上存在多种用于制备颗粒泡沫的方案。
WO2019/038213描述了一种方法，在该方法中将由80重量％至99.5重量％的PEI、0.5重量％至10重量％的发泡剂和0重量％至10重量％的添加剂组成的组合物借助于具有孔板的挤出机加工成发泡的或可发泡的粒料。在进料区和螺杆尖端之间的温度优选在320至400℃之间的范围内。此外，通常在这个区段内不存在均一的温度，而是相反，例如，在聚合物熔体的传送方向上存在具有升高的温度的梯度。所述孔板的温度在250至350℃之间，和当穿过所述孔板离开时，物料温度在230至360℃之间。在此通常在挤出机中进行加载所述发泡剂。所述粒料然后在离开所述孔板时经历发泡，前提是在所述水下造粒中的压力低于所述发泡剂的膨胀力。然后优选将膨胀的粒料进一步随后加工成颗粒泡沫模制件。由于这些泡沫珠通常具有非常低的密度，因此提到的方法特别对经济的运输具有负面影响。另外，在加工成模制件的过程中，总是必须将膨胀的颗粒泡沫压缩以避免缺陷和空腔，这不可避免地导致密度增加，并因此降低轻质构造的潜力。
WO 2019/025245描述了一种制备包含发泡剂并基于高温热塑性塑料的可膨胀粒料的方法。在该方法中，通过将玻璃化转变温度为至少180℃的聚合物熔融并将其与至少一种成核剂在挤出机中在300℃至350℃之间的温度下混合来制备聚合物熔体。在将发泡剂添加到所述聚合物熔体中后，将该熔体冷却到180℃至250℃之间的温度，输送穿过孔板并在水下造粒机中在75℃至99℃之间的水温下造粒。
必要的喷嘴温度相对于通常的水温(其为小于100℃)是非常高的。这导致喷嘴的冷却效果，并因此导致在所述喷嘴中聚合物熔体冻结的风险，特别是在方法启动时。
在Gloeckner和Müller发表在Kunststoffe，2，2016中的文章“Brillianten ausdem Reaktor(《来自反应器的亮点》)”中描述了一种意欲防止在挤出机喷嘴中聚合物熔体冻结的新方法。该文章提到了多种塑料。然而，没有讨论颗粒泡沫的制备，特别是由含有发泡剂的聚合物熔体制备颗粒泡沫。
发明内容
要解决的技术问题
鉴于现有技术，本发明要解决的技术问题是提供一种用于高温颗粒泡沫的新的造粒方法。
解决方案
所述问题通过提供一种使用水下造粒系统由包含至少一种聚合物的聚合物组合物制备(硬质)颗粒泡沫的方法来实现，所述聚合物具有至少180℃的根据ISO 11357-2(2014年7月出版)的玻璃化转变温度，所述方法的特征在于，
将挤出机的聚合物熔体
a)输送到加压的第一水回路中，其中压力在0.2至30巴范围内，和在所述水回路中的水温在105℃至180℃范围内，
b)造粒，和
c)任选地，供应到第二水回路中，该第二水回路具有低于100℃的温度并且在以下条件下运行
1)未加压，或
2)在0.2至30巴范围内的压力下。
在本发明的一个实施方案中，可将所述聚合物组合物在离开所述挤出机时引导到水下造粒机中。
在此，所述水下造粒机被设计为在一定温度和压力的组合下运行使得存在封闭的系统。根据本发明，在所述第一水回路中的温度为100℃至200℃。通过该方案，最大限度地减少了在所述聚合物熔体与在所述水下造粒机中的工艺水的温度之间的大温差。因此可以防止现有技术中描述的在喷嘴中聚合物熔体冻结的风险。
在常规方法中，将来自挤出机的聚合物熔体供应到在低于100℃水温下运行的水下造粒系统中。这导致粒料的突然冷却。因此，粒料颗粒在所述粒料的表面上形成凹痕或形成空泡。
已经令人惊奇地发现，根据本发明的方法控制产生以下结果：在所述第一水回路中升高的温度水平使得可以防止凹痕或空泡的形成。
根据本发明，加压的第一水回路优选在0.2至30巴，优选5至30巴，更优选3至10巴范围内的压力下运行。在所述第一水回路中的水温优选为105℃至180℃，更优选115℃至180℃。
该封闭的、加压的水循环系统使得可以在较高的水温下工作，同时减少操作人员暴露于热水蒸气。
造粒在所述第一个水回路中进行。这防止了现有技术中提到的粉尘形成和由于刮擦和锋利的切断边造成的粒料品质降低的缺点。
根据本发明，可将获得的粒料供应到第二水回路中，该第二水回路具有低于100℃的温度并且在未加压的情况下运行，或者在0.2至30巴的压力下运行。
当所述第二水回路根据方法步骤c)2)在压力下运行时，则在将所述粒料与所述工艺水分离之前将压力水平降低到环境压力。
可将所获得的粒料供应到干燥过程中。
干燥可以使用常规干燥机进行。适用于此目的的例如是离心式干燥机、循环空气干燥机、压缩空气干燥机、冲击式干燥机、带式干燥机、吸附式干燥机、带红外加热的旋转滚筒或含分子筛的干燥机。
在一个可另选的方法变型方案中，在方法步骤a)和b)之后，将获得的粒料立即从加压的第一回路中排出并供应到干燥过程中。当要在较高的温度水平下进一步处理所获得的粒料时，这是尤其令人感兴趣的。
在所述实施方案的另一个变型方案中，可借助于挤出机加工含有发泡剂的聚合物组合物。
在该变型方案中，将所述聚合物组合物在离开所述挤出机时引导到本发明的水下造粒机中。
在此，所述水下造粒机被设计为在一定温度和压力的组合下运行，从而使得防止发生发泡，例如通过使在步骤a)中的温度低于所述含有发泡剂的聚合物熔体的Tg至少5℃。这个方案提供了载有发泡剂的粒料，其可随后通过重新输入能量而发泡到希望的密度和/或通过任选的成型进一步加工成颗粒泡沫工件。
在所述第一水回路中存在的压力(其也称为背压)防止了发泡剂沸腾，从而防止了所述粒料发泡。
适用于这种方法的发泡剂选自挥发性有机化合物、无机发泡剂、可热分解发泡剂和上述物质的混合物，所述挥发性有机化合物在标准压力下的沸点低于基础材料的玻璃化转变温度。
在标准压力下的沸点低于基础材料的玻璃化转变温度且在标准温度(即25℃，1013毫巴)下是液体的挥发性有机化合物优选选自非卤代烃、酮、醇、卤代烃和上述物质的混合物。
所述酮优选选自丙酮、甲乙酮、环己酮、环壬酮、双丙酮醇和上述物质的混合物。所述酮更优选选自丙酮、甲乙酮和上述物质的混合物。
具有至少180℃的根据ISO 11357-2的玻璃化转变温度的合适聚合物选自聚砜或聚酰亚胺，特别是聚醚砜(PESU)、聚苯砜(PPSU)、聚砜(PSU)，聚醚酰亚胺(PEI)、热塑性聚酰亚胺和它们的混合物。基于PEI和聚醚醚酮(PEEK)的共混物的颗粒泡沫也是合适的。
除非另有说明，所述的玻璃化转变温度根据本发明是通过DSC(差示扫描量热法)测量的。本领域技术人员会意识到，只有在以下情况下DSC才提供了充分有说服力的信息：在第一次加热循环直至为比材料的最高玻璃化转变温度或熔融温度高最小25℃，但低于材料的最低分解温度至少20℃的温度后，将材料样品保持在该温度下至少2分钟。然后将所述样品再次冷却回到低于待测定的最低玻璃化转变温度或熔融温度至少20℃的温度，其中冷却速率应不超过20℃/分钟，优选不超过10℃/分钟。在另外等待几分钟后，再进行实际测量，其中将所述样品以通常10℃/分钟或更小的加热速率加热直到高于最高熔融温度或玻璃化转变温度至少20℃。
在用于制备颗粒泡沫的另一个方法变型方案中，加工包含成核剂的相应聚合物组合物。
这种任选的成核剂优选选自滑石、石墨、炭黑、二氧化钛和上述物质的混合物。所述任选的成核剂有利地改进了泡孔形态。
所述聚合物组合物含有基于总质量计0.01至3重量％，优选0.05至1重量％的成核剂。
根据本发明制备的粒料被进一步加工成(硬质)颗粒泡沫。
在此，(硬质)颗粒泡沫是指泡沫、硬质泡沫、颗粒泡沫和硬质颗粒泡沫，它们是基于具有至少180℃的根据ISO 11357-2的玻璃化转变温度的聚合物制备的。
由于所述粒料的品质更好，特别是在所述粒料中或在所述粒料表面上的缺陷最小化，因此获得了具有特别均一孔尺寸分布的(硬质)颗粒泡沫。
根据本发明的方法由至少一种具有至少180℃的根据ISO11357-2的玻璃化转变温度的聚合物制备的(硬质)颗粒泡沫可用于航天器或航空器的构造，造船，轨道车辆构造或车辆构造中，特别是在电动汽车中，在其外部构件中。这些(硬质)颗粒泡沫还可用于制备复合材料，所述复合材料同样可在所述应用中使用。
从至少一种具有至少180℃的根据ISO 11357-2的玻璃化转变温度的聚合物构成的(硬质)颗粒泡沫此外也特别适合于引入到航空器外部区域中。所述“外部区域”在此不仅意味着在航空器外皮中的填充物，而且还尤其意味着在飞机机头中、在尾部区域中、在机翼中、在外门中、在方向舵(Rudern)中或者在旋翼叶片中。
特别地，由于难燃性，根据本发明制备的(硬质)颗粒泡沫和复合材料也可被安装在所述车辆的内部空间中。
基于具有至少180℃的根据ISO 11357-2的玻璃化转变温度的聚合物的(硬质)颗粒泡沫特别适合于引入到航空器内部区域中。除了喷气式飞行器或轻型飞行器外，航空器尤其还包括直升机或者甚至航天器。在这样的航空器内部空间中的安装的实例例如是可在客机座椅后侧向下折叠的桌板、用于座椅或内部隔挡的填充物，以及例如内部门中。
本发明的方法和采用该方法产生的(硬质)颗粒泡沫特别适用于高温应用。
具体实施方式
实施例
实施例1
Ultem 1000型聚醚酰亚胺的水下造粒
将聚醚酰亚胺(PEI)(Ultem 1000，SABIC，荷兰)装载到挤出机(自动单螺杆APME1-180)的储料容器中，所述聚醚酰亚胺(PEI)具有根据ISO 11357-2(2014年7月出版)测量的217℃的玻璃化转变温度。在约370-375℃和15巴的压力下进行挤出。物料通过量为160kg/h。将熔体经由孔板供应到水下造粒系统(SPHERO 70，MAAG Automatik GmbH，德国)中。在所述孔板上游的喷嘴中的压力为约195巴。用9个刀在2000 1/分钟下进行造粒。
所述水下造粒在两个工艺水回路中进行。在第一高温回路中，工艺水温度为约140℃，压力为约4.95巴。在第二回路中，工艺水温度为约70℃，压力为约2.5巴。在所述两个回路中的停留时间各自约为8秒。
然后将粒料在离心式干燥机(CENTRO 300，MAAG Automatik GmbH，德国)中干燥。残留水分含量为0.30至0.47％。

Claims (11)

1.使用水下造粒系统制备(硬质)颗粒泡沫的方法，其由包含至少一种聚合物的聚合物组合物进行，所述聚合物具有至少180℃的根据ISO 11357-2(2014年7月出版)的玻璃化转变温度，其特征在于，
将挤出机的聚合物熔体
a)输送到加压的第一水回路中，其中压力在0.2至30巴范围内，和在所述水回路中的水温在105℃至180℃范围内，
b)造粒。
2.根据权利要求1所述的使用水下造粒系统制备(硬质)颗粒泡沫的方法，其特征在于，
将挤出机的聚合物熔体
a)输送到加压的第一水回路中，其中压力在0.2至30巴范围内，和在所述水回路中的水温在105℃至180℃范围内，
b)造粒，和
c)供应到第二水回路中，该第二水回路具有低于100℃的温度并且在以下条件下操作
1)未加压，或
2)在0.2至30巴范围内的压力下。
3.根据权利要求1所述的制备(硬质)颗粒泡沫的方法，其特征在于，所述具有至少180℃的根据ISO 11357-2的玻璃化转变温度的聚合物选自聚砜或聚酰亚胺，特别是聚醚砜(PESU)、聚苯砜(PPSU)、聚砜(PSU)，聚醚酰亚胺(PEI)、热塑性聚酰亚胺和它们的混合物。
4.根据权利要求1所述的制备(硬质)颗粒泡沫的方法，其特征在于，所述聚合物组合物包含发泡剂。
5.根据权利要求3所述的制备(硬质)颗粒泡沫的方法，其特征在于，在步骤a)中的温度比所述含有发泡剂的聚合物熔体的Tg低至少5℃。
6.根据权利要求3所述的制备(硬质)颗粒泡沫的方法，其特征在于，所述发泡剂选自挥发性有机化合物、无机发泡剂、可热分解发泡剂和上述物质的混合物，所述挥发性有机化合物在标准压力下的沸点低于基础材料的玻璃化转变温度。
7.根据权利要求1所述的制备(硬质)颗粒泡沫的方法，其特征在于，所述聚合物组合物包含成核剂。
8.根据权利要求6所述的制备(硬质)颗粒泡沫的方法，其特征在于，所述成核剂选自滑石、石墨、炭黑、二氧化钛和上述物质的混合物。
9.根据权利要求1所述的制备(硬质)颗粒泡沫的方法，其特征在于，在步骤b)后将所获得的粒料排放并供应到干燥过程中。
10.根据权利要求1所述的制备(硬质)颗粒泡沫的方法，其特征在于，将所获得的粒料在步骤c)后排放并供应到干燥过程中。
11.通过根据权利要求1所述的方法制备的(硬质)颗粒泡沫在航空航天工业、造船、车辆构造中的用途，特别是在电动汽车中的用途。
CN202180050687.8A 2020-08-18 2021-07-15 通过在升高的水温下进行水下造粒制备基于高温聚合物的粒料以制备（硬质）颗粒泡沫 Pending CN115943026A (zh)

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