CN111032756A - 基于高温热塑性塑料的、可膨胀的含有发泡剂的颗粒 - Google Patents

基于高温热塑性塑料的、可膨胀的含有发泡剂的颗粒 Download PDF

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CN111032756A
CN111032756A CN201880050814.2A CN201880050814A CN111032756A CN 111032756 A CN111032756 A CN 111032756A CN 201880050814 A CN201880050814 A CN 201880050814A CN 111032756 A CN111032756 A CN 111032756A
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I·A·奎罗兹达丰塞卡
P·古特曼
J·布罗伊尔
G·格雷瑟尔
R·伯里
M·施密特
S·伯克哈特
A·凯勒
F·亨恩伯格
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Abstract

本发明涉及基于高温热塑性塑料的、可膨胀的含有发泡剂的球团，所述高温热塑性塑料的玻璃化转变温度根据ISO 11357‑2‑1999为至少180℃，可膨胀的含有发泡剂的颗粒含有至少一种成核剂并且堆积密度根据DIN ISO 697:1982为400至900kg/m3并且质量为1至5mg/球团，涉及制备其的方法和由其可获得的泡沫颗粒，该泡沫颗粒根据ISO 11357‑2‑1999的玻璃化转变温度为至少180℃，经膨胀的泡沫颗粒含有至少一种成核剂并且堆积密度根据DIN ISO 697:1982为10至200kg/m3，涉及由其可获得的颗粒泡沫及其用于生产航空部件的用途。

Description

基于高温热塑性塑料的、可膨胀的含有发泡剂的颗粒
本发明涉及基于高温热塑性塑料的、可膨胀的含有发泡剂的球团，所述球团的堆积密度根据DIN ISO 697：1982为400至700kg/m3，并且其质量为1至5mg/球团，涉及制备其的方法和经膨胀的泡沫颗粒和由其可获得的颗粒泡沫，以及其在生产航空部件中的用途。
WO 2013/092689记载了一种通过挤出负载有发泡剂的聚苯醚砜(PPSU)的聚合物熔体来制备泡沫板的方法。优选使用异丙醇的混合物作为发泡剂。将获得的泡沫板随后在真空和升高的温度下在模具中进行发泡以提供成型的泡沫模制品。
WO 2014/057042记载了一种基于聚醚砜的混合物、具有均匀的孔尺寸分布的耐高温的泡沫。
EP 1 333 051 A2记载了一种由耐高温的聚砜或聚醚砜制备泡沫网的方法，其通过将聚砜或聚醚砜和挥发性的发泡剂的混合物泡沫挤出而进行。优选使用水或水和醇或酮的混合物作为发泡剂。
EP 0 411 437记载了一种制备基于聚芳基醚砜的可膨胀球团的方法，所述基于聚芳基醚砜的可膨胀球团包含基于球团计5重量％至20重量％的甲基乙基酮或丙酮作为发泡剂，其中发泡剂和聚合物在挤出机中在机筒温度为至少50℃且至多170℃下混合，随后直接挤出至温度低于40℃的介质中。该方法仅限于低吞吐量。将球团在阳模中压成10mm厚的含有发泡剂的板，随后将其发泡成20cm厚的泡沫块。孔径为0.2至0.8mm。
WO 2016/052604和EP 3 202 837 A1记载了通过烧结泡沫颗粒生产颗粒泡沫的方法，所述泡沫颗粒由玻璃化转变温度为至少180℃的聚合物，特别是聚醚砜(PESU)、聚醚酰亚胺(PEI)、聚苯砜(PPSU)或聚砜(PSU)制得。所述泡沫颗粒优选密度为40至900kg/m3且平均孔径为180-1500μm。由此得到的颗粒泡沫具有33％至64％的高的开孔量(open-cellcontent)。
本发明的目的是提供储存稳定的、可膨胀的球团，其基于耐高温的聚合物，特别是聚醚砜，所述球团随着数周的储存时间表现出低的发泡剂损失，并且可以经发泡/熔接得到具有低密度的泡沫颗粒或颗粒泡沫。此外，可膨胀的球团应当以高吞吐量获得，并且应当可以易于加工成具有均匀的细孔结构的颗粒泡沫。
该目的通过权利要求1的基于高温的热塑性塑料的、可膨胀的含有发泡剂的球团和权利要求3的经膨胀的泡沫颗粒来实现。
优选的实施方案在从属权利要求中提出。
可膨胀的球团优选是球形的。球形应被理解为意指没有任何角或边的球团，例如为圆柱形挤压式球团的特征。球形球团的最短直径与最长直径的比值优选为0.9至1.0，特别优选为0.95至0.99。由于其球面，优选的可膨胀的含有发泡剂的球团和可通过预发泡获得的泡沫颗粒易于通过气动的传输装置输送和注入泡沫模具中。
本发明的基于高温热塑性塑料的、可膨胀的含有发泡剂的球团的堆积密度根据DIN ISO 697：1982为400至900kg/m3，优选为450至700kg/m3且特别优选为500至680kg/m3。它们的质量为1至10mg/球团，优选2至4mg/球团。
合适的高温热塑性塑料是玻璃化转变温度为至少180℃，优选200至240℃的热塑性聚合物，所述玻璃化转变温度根据ISO 11357-2-1999(E)通过DSC测定，加热速率为10K/min。高温热塑性塑料优选为至少一种聚醚砜或具有不同重均分子量Mw或具有不同粘度值的聚醚砜的混合物。优选使用粘度值为46至50cm3/g的聚醚砜和粘度值为54至58cm3/g的聚醚砜的混合物，所述粘度值根据ISO 307,1157,1628(在0.01g/ml苯酚/1，2-邻二氯苯，1：1)测定。
作为发泡剂，可膨胀的球团包含3至15重量％，优选5至10重量％的具有1至4个碳原子的醇、酮或烃，优选丙酮、甲基乙基酮、乙醇、异丙醇、异丁烷、水或它们的混合物，其中可膨胀的球团特别优选包含3至10重量％的丙酮。
现已出乎预料地发现，可膨胀球团的堆积密度对于发泡剂容量/储存稳定性具有影响，因此还影响了预发泡过程中可实现的密度降低。
可膨胀的球团和经膨胀的泡沫颗粒均优选含有滑石、二氧化钛、石墨、炭黑或其混合物作为成核剂。可膨胀的球团和经膨胀的泡沫颗粒均优选含有0.01重量％至2.0重量％，特别优选0.05重量％至1.5重量％的滑石、二氧化钛、石墨、炭黑或其混合物作为成核剂，基于高温热塑性塑料和成核剂的总和计。
可膨胀的球团和经膨胀的泡沫颗粒均优选仅仅排他性地包含至少一种聚醚砜作为高温热塑性塑料。
本发明还提供一种制备基于高温热塑性塑料的、可膨胀的含有发泡剂的球团的方法，其包括以下步骤：
a)通过熔融至少一种根据ISO 11357-2-1999的玻璃化转变温度为至少180℃的聚合物，并且将其与至少一种成核剂在挤出机中在300℃至350℃的温度下混合来制备聚合物熔体，
b)向聚合物熔体中加入发泡剂，
c)将聚合物熔体冷却至180℃至250℃的温度，
d)任选地通过齿轮泵输送聚合物熔体，
e)在180℃至250℃的温度下，通过多孔板输送负载有发泡剂的聚合物熔体，并在水下造粒机中将负载有发泡剂的聚合物熔体造粒，水下造粒机在75℃至99℃的水温下、在10至20bar的压力下操作。
步骤b)和c)可以同时进行或相继进行。步骤c)优选在步骤b)之后进行。这意味着通过加入发泡剂和/或外部冷却将含有发泡剂的聚合物熔体冷却至180℃至250℃的温度。以此方式，含有发泡剂的聚合物熔体可以被输送通过受热的多孔板，并在180℃至250℃的熔体温度下造粒。
作为发泡剂，本发明的方法可以使用3至15重量％，优选5至10重量％的具有1至4个碳原子的醇、酮或烃，优选丙酮、甲基乙基酮、乙醇、异丙醇、异丁烷、水或它们的混合物，基于包含其添加剂的聚合物熔体计。特别优选向聚合物熔体中添加3至10重量％的丙酮。
成核剂或阻燃剂可以加入聚合物熔体中作为添加剂。优选使用滑石、二氧化钛、石墨、炭黑或其混合物。
本发明方法使用上述热塑性塑料作为高温热塑性塑料。高温热塑性塑料优选为至少一种聚醚砜或具有不同重均分子量Mw或具有不同粘度值的聚醚砜的混合物。优选使用粘度值为46至50cm3/g的聚醚砜和粘度值为54至58cm3/g的聚醚砜的混合物，所述粘度值根据ISO 307，1157,1628(在0.01g/ml苯酚/1，2-邻二氯苯，1：1)测定。
可膨胀球团的400至900kg/m3的高堆积密度可通过水下造粒中的高水压和发泡剂的选择及其浓度，以及结合水下造粒的挤出装置中的温度分布来实现。
本发明还提供基于高温热塑性塑料的经膨胀的泡沫颗粒，其中可膨胀的含有发泡剂的球团含有至少一种成核剂，并且其堆积密度根据DIN ISO 697：1982为10至200kg/m3。
本发明的经膨胀的泡沫颗粒的平均孔径通常为30至150μm，优选为50至100μm。优选90％的孔、特别优选99％的孔，具有小于150μm的孔径。平均长度/宽度比优选低于2.0，特别优选低于1.6。
这些可通过使可膨胀的颗粒预发泡而获得。合适的是，这样一种制备基于高温热塑性塑料的泡沫颗粒的方法，所述方法包括在180℃至280℃，优选220℃至250℃的温度下，将上述可膨胀的含有发泡剂的球团例如在循环空气烘箱中发泡5至300秒，优选10至150秒。
可以将由此获得的经膨胀的泡沫颗粒熔接以获得颗粒泡沫模制品。合适的是，这样一种制备基于高温热塑性塑料的颗粒泡沫的方法，其中将上述可膨胀的含有发泡剂的球团或经膨胀的泡沫颗粒在模具中用蒸汽、热空气、IR或电磁辐射或热压进行熔接。
由此获得的颗粒泡沫通常是闭孔泡沫。所述颗粒泡沫的密度优选为20至250kg/m3，特别优选40至150kg/m3。
本发明的泡沫颗粒尤其适于用于航空应用的复合板。
由于本发明的可膨胀的含有发泡剂的球团的高堆积密度和基于发泡剂损失少而具有的良好的储存稳定性，所述球团可以以低的运输成本——即使是相对较长的运输路线——运输给加工者，他们可以将所述球团预发泡成经膨胀的泡沫颗粒，并随后加工成具有任意期望的三维形状的泡沫模制品。
实施例
所用原料：
PESU
Ultrason E0510 聚醚砜(PESU)，来自BASF SE，密度为1370kg/m3，粘度值为40cm3/g(在0.01g/ml苯酚/1，2-邻二氯苯，1：1)，玻璃化转变温度DSC(10℃/min)222℃)
Ultrason E1010 聚醚砜(PESU)，来自BASF SE，密度为1370kg/m3，粘度值为48cm3/g(在0.01g/ml苯酚/1，2-邻二氯苯，1：1)，玻璃化转变温度DSC(10℃/min)222℃)
Ultrason E2010 聚醚砜(PESU)，来自BASF SE，密度为1370kg/m3，粘度值为56cm3/g(在0.01g/ml苯酚/1，2-邻二氯苯，1：1)，玻璃化转变温度DSC(10℃/min)225℃)
滑石Microtalk IT extra，Mondo Minerals，平均粒度d50％<2μm)
石墨Graphit Kropfmühl AG，平均粒度d50％＝4.8μm)
TiO2Kronos 2220，CAS 13463-67-7
发泡剂 丙酮(丙酮99.97％(平衡水)Firma Domo)
分析：
含有发泡剂的可膨胀的球团的堆积密度根据DIN ISO 697：1982确定。
通过重量分析方法将可膨胀的球团中的发泡剂含量确定为挥发性组分。为此，将约20g的含有发泡剂的球团称重至铝盘中，在250℃下在循环空气烘箱中干燥至少2小时并再次称重。
压缩应力根据DIN EN ISO 844：2014确定。
通过使用相机拍摄泡沫颗粒的横截面并用来自Goldlücke Ingenieurleistungen的PORE！SCAN进行评估来确定孔的尺寸分布和平均孔径。为此，用双面胶带将10个泡沫颗粒粘在刨花板(10×10cm)上，并从中间切开。为了确定平均孔面积和平均孔径，评估约1500个孔。
实施例1-26：
通过熔融浸渍法生产可膨胀的PESU球团
熔体浸渍在由以下设备组成的装置中进行：来自Leistritz的双螺杆挤出机，该挤出机分为八个等长区域(Z1...Z8)，螺杆直径为18mm，长径比为40；熔体泵(齿轮泵GP)；导流阀(DV)；熔体过滤器；多孔板(DP)和水下造粒机(UWP)。
将聚醚砜(PESU)与添加剂(滑石、二氧化钛、石墨)在聚乙烯袋中混合，计量加入双螺杆挤出机中并熔融。在挤出机长度的约2/3处，使用Isco泵(来自Axel Semrau的柱塞泵)和内置在挤出机中的注入器将发泡剂注入挤出机的Z5区域中。从Z6区开始，通过双螺杆挤出机的温度控制装置冷却聚合物熔体。聚合物熔体通过多孔板时的温度对应于区域8中设定的温度。使用熔体泵(GP)调节挤出机中的压力分布(控制压力-速度)，使发泡剂完全混入聚合物熔体中。除了在双螺杆挤出机中调节压力曲线外，熔体泵还用于将浸渍了发泡剂的聚合物熔体输送通过下游设备(导流阀、熔体筛和多孔板)。在水下造粒机(UWP)的压力下，将通过多孔板(1个孔的直径为1.0毫米)排出的成股的熔体切割成球团重量约为2.3mg的可膨胀的聚醚砜球团。挤出机的总吞吐量保持为5kg/h不变。水箱中的成股材料用连接成一个刀环的10片刀切开。在实施例1-12中，刀环以3600rpm的转速旋转。这形成球团重量为2.3mg的可膨胀球团，这些球团通过水循环从多孔板输送到干燥机中，然后从那里沉积至收集容器(此处为锡罐)中。
表1记录了所用原料的重量份。重量份基于100重量％的固体(不含发泡剂的聚合物和添加剂)。发泡剂的份数基于100重量％的固体(聚合物和添加剂)。表2记录了工艺参数。温度是在装置各部分中所设定和测量的温度值。
在实施例1-12、17、20-24中使用丙酮作为发泡剂。在实施例13-16和18-19中，使用表1中记录的重量比的丙酮和水、乙醇或异丙醇的混合物。
在实施例13-23中，将刀速设定为表2中所记录的数值。获得的球团重量为2.8mg(3000rpm)、2.4mg(3500rpm)和3.3mg(2500rpm)。
对比例V1和V2
在对比例V1和V2中，含有发泡剂的聚合物熔体的温度保持恒定并且不进行冷却。
表1：实施例1-12和对比实验V1和V2所用的原料，采用100重量％的固体和额外的发泡剂
Figure BDA0002379843860000081
Figure BDA0002379843860000091
Figure BDA0002379843860000101
表3：生产后可膨胀球团的堆积密度和随着储存时间可膨胀球团中发泡剂的浓度的变化
Figure BDA0002379843860000111
生产PESU泡沫颗粒
如下将来自实施例1-3的可膨胀的球团在循环空气烘箱中发泡成泡沫颗粒。
1.)将烘箱设定成230℃，因为否则要花费太长的时间才能达到220℃的温度，并将2个铝盘(约500ml)置于烘箱中，同样也要达到该温度。
2.)一旦烘箱显示225℃的温度，通过打开烘箱门，将球团从握成杯状的手中或小的塑料容器中倒入铝盘，从而在两个铝盘中分配约6g的可膨胀球团。注意颗粒不要堆积。
烘箱门的打开引起烘箱内的温度降低约5℃至220℃。230℃的设定也确保温度不会进一步下降。
3.)一旦关闭烘箱就启动秒表，在规定时间(此处为60s和120s)后，再次打开该门，取出装有可膨胀球团的铝盘，并将其置于实验台上冷却。
4.)一旦装有球团的铝盘冷却，堆积密度以类似于DIN ISO 697：1982测定。方法是类似的，因为使用50ml的量杯，这是由于根据标准精确地测量将不得不需要太多的尚待发泡的球团。
使可膨胀的球团发泡后1周，所测得的堆积密度示于表4中。
图1示出了根据实施例1，发泡至81g/l的密度的泡沫颗粒的具有孔分布情况的横截面。平均孔径为64μm。99％的孔的孔径小于150μm，90％的孔的孔径小于110μm。孔的平均长度/宽度比值为1.4。
表4：发泡前和发泡后一周的堆积密度
Figure BDA0002379843860000121
生产PESU颗粒泡沫板
将来自实施例19-22的泡沫颗粒装入内部尺寸为200×300×12mm的模具中，并且在高压模制机中使用蒸汽进行熔接以得到泡沫板。在不同压缩率下的密度和压缩应力记录于表5中。
表5：泡沫板的机械性能
Figure BDA0002379843860000131

Claims (14)

1.基于高温热塑性塑料的、可膨胀的含有发泡剂的球团，所述高温热塑性塑料的玻璃化转变温度根据ISO 11357-2-1999为至少180℃，其中可膨胀的含有发泡剂的球团包含至少一种成核剂并且堆积密度根据DIN ISO 697:1982为400至900kg/m3并且质量为1至10mg/球团。
2.权利要求1的可膨胀球团，其中其包含3至15重量％的丙酮。
3.基于高温热塑性塑料的经膨胀的泡沫颗粒，所述高温热塑性塑料根据ISO 11357-2-1999的玻璃化转变温度为至少180℃，其中经膨胀的泡沫颗粒包含至少一种成核剂并且堆积密度根据DIN ISO 697:1982为10至200kg/m3。
4.权利要求3的经膨胀的泡沫颗粒，其中其包含0.01重量％至2.0重量％的滑石、二氧化钛、石墨、炭黑或其混合物作为成核剂，基于高温热塑性塑料和成核剂的总和计。
5.权利要求1或2的可膨胀的泡沫颗粒或权利要求3至5中任一项的经膨胀的泡沫颗粒，其中其由作为高温热塑性塑料的至少一种聚醚砜制得。
6.一种制备基于高温热塑性塑料的、可膨胀的含有发泡剂的球团的方法，其包括以下步骤：
a)通过熔融至少一种根据ISO 11357-2-1999的玻璃化转变温度为至少180℃的聚合物，并且将其与至少一种成核剂在挤出机中在300℃至350℃的温度下混合来制备聚合物熔体，
b)向聚合物熔体中加入发泡剂，
c)将含有发泡剂的聚合物熔体冷却至180℃至250℃的温度，
d)任选地通过齿轮泵输送聚合物熔体，
e)在180℃至250℃的温度下，通过多孔板输送含有发泡剂的聚合物熔体，并在水下造粒机中将负载有发泡剂的聚合物熔体造粒，水下造粒机在75℃至99℃的水温下、在10至20bar的压力下操作。
7.权利要求6的方法，其中丙酮、异丁烷、乙醇、异丙醇、水或其混合物用作发泡剂。
8.权利要求6或7的方法，其中滑石、二氧化钛、石墨、炭黑或其混合物用作成核剂。
9.权利要求6至8中任一项的方法，其中至少一种聚醚砜用作聚合物。
10.权利要求6至9中任一项的方法，其中将具有不同平均分子量Mw的聚醚砜的混合物用作聚合物。
11.制备基于高温热塑性塑料的泡沫颗粒的方法，其中将权利要求1或2的可膨胀的含有发泡剂的球团在180℃至280℃的温度下发泡5至300秒。
12.制备基于高温热塑性塑料的颗粒泡沫的方法，其中将权利要求3至5中任一项的经膨胀的泡沫颗粒在模具中用蒸汽、热空气、IR或电磁辐射或热压进行熔接。
13.可通过权利要求12的方法获得的颗粒泡沫，其密度为20至250kg/m3。
14.权利要求13的颗粒泡沫用于生产航空部件的用途。
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