CN111350883A - 流体输送管道及其用途 - Google Patents

流体输送管道及其用途 Download PDF

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Publication number
CN111350883A
CN111350883A CN201911290802.XA CN201911290802A CN111350883A CN 111350883 A CN111350883 A CN 111350883A CN 201911290802 A CN201911290802 A CN 201911290802A CN 111350883 A CN111350883 A CN 111350883A
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weight
fluid
fluid transfer
transfer conduit
particularly preferably
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CN111350883B (zh
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海因茨·卡维耶泽尔
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EMS Patent AG
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EMS Patent AG
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    • F16L9/12—Rigid pipes of plastics with or without reinforcement
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    • B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
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Abstract

本发明涉及一种流体输送管道，该流体输送管道具有与流体接触的内层以及至少一个直接与内层连接的外层，该内层包括至少一种脂肪族聚酰胺和至少一种抗冲改性剂，且该外层由脂肪族聚酰胺和至少一种阻燃剂形成。内层保证相对于待输送流体的耐化学性和机械阻力，而外层保证阻燃性。

Description

流体输送管道及其用途
技术领域
本发明涉及一种流体输送管道，该流体输送管道具有与流体接触的内层以及至少一个直接与内层连接的外层，该内层包括至少一种脂肪族聚酰胺和至少一种抗冲改性剂，且该外层由脂肪族聚酰胺和至少一种阻燃剂形成。内层保证相对于待输送流体的耐化学性和机械阻力，而外层保证阻燃性。
背景技术
液体的输送，特别是在汽车领域，需要使用特定的材料。根据材料和规格，此类输送管道必须通过一系列测试。特别是在冷却剂的输送中，要满足的规格是严格的。水溶液的供应，通常是水-乙二醇混合物的供应要求与水溶液接触的组分具有耐水解性。
在电动汽车领域中还涉及特别高的规格。因此，锂离子电池的电化学反应仅仅可能在规定的温度范围内发生。电动汽车中的这种蓄电池通常在20℃至30℃的温度运行。当温度超过30℃，这种电池的老化呈指数级增加。在40℃以上的温度下，还会对电池造成永久性损坏。另外，电池过热可能导致起火的危险，从而可能导致车辆意外损坏。
通常，这些管道由阻燃材料组成或至少具有阻燃剂层。根据EP 1265749已知其中使用了基于聚烯烃的阻燃层的这种多层管道。
JP 1269536公开了一种基于聚酰胺的柔性管道。该管道具有两层结构，外层由PA11或PA12形成，内层由阻燃弹性体共聚酰胺形成。
在这种多层结构的情况下，通常使用黏合剂层以实现阻燃材料和芯材料之间的黏结。然而，这必然随之导致这些部件的制造相当复杂并且导致部件的重量更高。这种部件的减重是制造中特别重要的方面，特别是在汽车工业中的应用中。
发明内容
因此，本发明的目的是提供流体输送管道，该流体输送管道克服了现有技术中已知的缺点，并且相对于待输送的流体具有良好的耐化学性，同时具有良好的机械性能和阻燃性能，并且流体管道重量轻。另外，应尽可能降低这些管道的生产复杂性。
该目的通过具有权利要求1的特征的流体输送管道和具有权利要求16的特征的该流体输送管道的用途来实现。进一步的从属权利要求显示其有利的实施方案。
根据本发明，提供了流体输送管道，其包括以下层：
·与流体接触的内层，其由包含至少一种脂肪族聚酰胺和至少一种抗冲改性剂的模塑料形成，该至少一种聚酰胺的氨基端基浓度为30mmol/kg至90mmol/kg，和
·直接与内层连接的至少一个外层，其由包含至少一种脂肪族聚酰胺的具有至少一种阻燃剂的模塑料形成。
从本发明的意义上说，术语“聚酰胺”(缩写为PA)应理解为一种包括均聚酰胺和共聚酰胺的上位概念。用于聚酰胺和其单体的所选拼写和缩写对应于在ISO标准16396-1(2015,(D))中指定的那些。其中在单体的IUPAC名称之后使用的缩写与单体的IUPAC名称同义使用。
内层和外层的聚酰胺优选选自PA12、PA612、PA1010、PA106、PA1016、PA1012、PA614、PA615、PA616、PA618、PA1212、PA610、PA11和其共聚酰胺、混合物和共混物，优选PA12、PA11、PA610、PA612和PA11，特别优选PA12，内层和外层优选包含相同类型的聚酰胺。
优选地，聚酰胺的氨基端基浓度为30mmol/kg至80mmol/kg，优选为35mmol/kg至75mmol/kg，特别优选为40mmol/kg至60mmol/kg。由此以电位方式进行端基浓度的确定。优选地，氨基端基浓度大于羧基端基浓度。
一个优选实施方案规定，至少一种阻燃剂是无卤素的阻燃剂。因此特别优选有机阻燃剂。特别地，使用选自以下的阻燃剂：
·三聚氰胺与氰尿酸的转化产物，
·三聚氰胺的缩合产物，特别是蜜勒胺、蜜白胺、聚[(8-氨基-1,3,4,6,7,9,9b-七氮杂非那烯-2,5-亚基)亚氨基]，
·三聚氰胺与多磷酸的转化产物，
·三聚氰胺的缩合产物与多磷酸的转化产物，
·金属次膦酸盐
·磷酸酯
和/或其混合物。
特别地，所述阻燃剂选自氰尿酸三聚氰胺、磷酸三聚氰胺、焦磷酸三聚氰胺、多磷酸三聚氰胺、磷酸蜜勒胺、焦磷酸蜜勒胺、焦磷酸二三聚氰胺、磷酸二三聚氰胺、多磷酸聚[(8-氨基-1,3,4,6,7,9,9b-七氮杂非那烯-2,5-亚基)亚氨基]、磷杂菲及其混合物。
优选地，至少一种金属次膦酸盐选自次膦酸盐、二次膦酸盐及其组合。特别优选涉及通式(I)的次膦酸盐
Figure BDA0002316628890000031
和/或式(II)
Figure BDA0002316628890000032
和/或其聚合物
其中
R1、R2相同或不同，优选为直链的或带支链的C1至C8烷基和/或芳基；
R3为直链的或带支链的C1至C10亚烷基、C6至C10亚芳基、
-烷基亚芳基或芳基亚烷基；
M是元素周期表的第2或第3主族或副族中的金属离子；并且
m表示2或3；
n表示1或3；
x表示1或2。
作为金属离子M，优选使用Al、Ca和Zn。
因此，相对于模塑料的重量，外层分别优选地包含5重量％至30重量％，优选10重量％至25重量％，特别优选11重量％至20重量％的至少一种阻燃剂。
优选的是至少一种抗冲改性剂是官能化的抗冲改性剂，选自乙烯-丙烯共聚物、乙烯-1-丁烯共聚物、乙烯-丙烯-1-丁烯共聚物、苯乙烯共聚物、苯乙烯嵌段共聚物及其混合物。
可以通过共聚作用或通过接枝使抗冲改性剂官能化。在本发明的意义上，通过共聚作用的官能化是指在组分(C)的主链中引入官能化化合物作为该主链的组分。相反，应理解组分(C)的官能化是通过将官能化化合物接枝、结合至主链，从而产生侧链来进行的。
优选地，在内层中包含0.1重量％至30重量％、优选5重量％至25重量％、特别优选10重量％至20重量％的量的至少一种抗冲改性剂。
还优选的是外层包含选自以下的其他添加剂：
(i)0重量％至15重量％，优选2重量％至12重量％，特别优选4重量％至10重量％的至少一种增塑剂，
(ii)0.1重量％至2重量％，优选0.2重量％至1.5重量％，特别优选0.3重量％至1重量％的至少一种稳定剂，特别是热稳定剂，
(iii)0重量％至5重量％，优选0.1重量％至4重量％，特别优选0.2重量％至3.5重量％的选自UV稳定剂、导热添加剂、阻燃增效剂、加工助剂、润滑剂、着色和标记材料、无机颜料、有机颜料、IR吸收剂、膨胀剂、和/或其混合物的至少一种其他添加剂，
相对于模塑料的重量，添加剂(i)至(iii)的总和为0.1重量％至22重量％。
组分(i)的增塑剂优选选自具有2个至12个C原子的芳基磺酸的酰胺、在醇组分中构成的具有2个至20个C原子的对羟基苯甲酸的酯、膦酸盐/酯或磷酸盐/酯，优选地，增塑剂由芳基砜酰胺组成。
优选的含磷增塑剂尤其是磷酸二苯基甲苯基酯(Disflamol DPK)、磷酸三(2-乙基己基)酯、二苯基-2-乙基己基磷酸酯、磷酸三甲苯基酯、烷基或芳基膦酸酯、膦酸二乙酯或环状膦酸酯，例如Aflammit PLF 710。
优选的4-羟基苯甲酸的酯是对羟基苯甲酸辛酯、对羟基苯甲酸乙酯、对羟基苯甲酸-1-十六烷基酯、对羟基苯甲酸-2-己基癸酯。
优选地，形成外层的模塑料具有根据ISO 307测量的1.6至1.9的相对黏度，并且形成内层的模塑料具有根据ISO 307测量的1.8至2.3的相对黏度。
优选外层的厚度为0.1mm至1.5mm，优选为0.12mm至1.4mm，特别优选为0.15mm至1.3mm。
内层的厚度或结构取决于模塑品类型例如管道或软管，并且可以相应地选择。在此，厚度优选为0.5mm至2.5mm，特别优选为0.75mm至1.6mm。
此外，优选的是，流体输送管道在内层和外层之间没有黏合剂层，并且优选地由内层和外层组成。这尤其是通过对内层和外层使用相同类型的聚酰胺例如PA12来实现的。结果，实现了内层和外层之间的独立黏合。
优选将液体，优选冷却剂，特别优选水-醇混合物，特别是水-乙二醇混合物用作流体。
优选地，流体输送管道以光滑管道或起伏管道的形式存在。
流体输送管优选是通过共挤出、吹塑和注塑由用于内层和外层的模塑料能够制备的。
根据本发明的流体输送管道用于供应流体或液体，优选水溶液的类型，特别优选冷却剂的类型，特别是水-醇混合物。
因此，优选地，流体输送管道用于在电动机或电池中，特别是用于在电动车辆中供应流体。
具体实施方式
参考以下实施例，旨在更详细的解释根据本发明的主题，而不希望将所述主题限制于这里所示的实施例。
实施例和比较例中使用的基体材料及其性能列于表1。
表1
Figure BDA0002316628890000061
在本发明的范围内使用以下测量方法；如果没有发现不同，则测试件在干燥状态下进行测试。
相对黏度
在20℃的温度下用0.5g聚合物在100ml合适溶剂(例如用于聚酰胺12的间甲酚)中根据ISO 307测定相对黏度。
挤出方法
在Nokia Maillefer COEX5管道挤出机上以9.5m/min的挤出速度并在165毫巴的真空下于240℃至250℃的高温下共挤出管道。将外径为15mm、内径为12mm、壁厚为1.5mm的管道用作测试件。
阻燃测试：
根据修改的UL-94测量方法来测量挤出管道的燃烧性能。将测试件在50％相对湿度下在23℃下存储48小时或在70℃下存储7天。对于每个结构，至少要进行三次测试。将挤出的管道(外径15mm；壁厚1.5mm)缩短到150mm区段。随后将管道垂直夹紧，并进行垂直燃烧测试。
摆锤冲击
根据DIN 73378在23±2℃下测量。
电位滴定法确定NH2端基
为了确定聚酰胺的NH2端基，将0.5g样品溶解在50ml间甲酚中，并在100℃下搅拌。加入25ml异丙醇和3ml其他溶液(在冰醋酸中的6g/l氨基己酸)后，用0.05M乙醇高氯酸溶液进行电位滴定。
根据以下公式计算NH2端基：
NH2(mmol/kg)：(a-b)*c*F*1000/E
其中
a针对含其他溶液的样品的0.05mol/l乙醇高氯酸的ml消耗量
b针对其他溶液的0.05mol/l乙醇高氯酸的ml消耗量
c乙醇高氯酸浓度(0.05mol/l)
F 0.05mol/l乙醇高氯酸的因子
E以g计的聚合物重量
在表2中，比较了根据本发明的测试件和对比测试件的机械性能和阻燃性能。
表2
Figure BDA0002316628890000081
n.c.：无法根据UL-94分类
结果讨论
根据本发明的实施例显示了特别良好的机械性能和阻燃性能的组合。只有用抗水解的热塑性塑料制成的内层才能保证在应用中保持机械性能。然而，如果将阻燃剂添加到抗水解模塑料中，则机械性能受到显著地不利影响。实际上，通过比较例1可以实现良好的机械性能，但是是以阻燃性能为代价的。如比较例3中所示，添加阻燃剂可达到根据UL-94的最佳分类V0，但是再次付出机械性能的代价。
相反，只有根据本发明的测试件显示出良好的机械性能，同时实现了根据UL-94的最佳分类V0。

Claims (17)

1.一种流体输送管道，其包括
·与流体接触的内层，其由包含至少一种脂肪族聚酰胺和至少一种抗冲改性剂的模塑料形成，至少一种聚酰胺的氨基端基浓度为30mmol/kg至90mmol/kg，和
·直接与内层连接的至少一个外层，其由包含至少一种脂肪族聚酰胺的具有至少一种阻燃剂的模塑料形成。
2.根据权利要求1所述的流体输送管道，
其特征在于所述内层和所述外层的聚酰胺选自PA12、PA612、PA1010、PA106、PA1016、PA1012、PA614、PA615、PA616、PA618、PA1212、PA610、PA11和其共聚酰胺、混合物和共混物，优选PA12、PA11、PA610、PA612和PA11，特别优选PA12，所述内层和所述外层优选包含相同类型的聚酰胺。
3.根据权利要求1或2所述的流体输送管道，
其特征在于所述聚酰胺的氨基端基浓度为30mmol/kg至80mmol/kg，优选为35mmol/kg至75mmol/kg，特别优选为40mmol/kg至60mmol/kg。
4.根据权利要求1至3中任一项所述的流体输送管道，
其特征在于至少一种阻燃剂是无卤素的阻燃剂，优选有机阻燃剂，特别优选选自：
·三聚氰胺与氰尿酸的转化产物，
·三聚氰胺的缩合产物，特别是蜜勒胺、蜜白胺、聚[(8-氨基-1,3,4,6,7,9,9b-七氮杂非那烯-2,5-亚基)亚氨基]，
·三聚氰胺与多磷酸的转化产物，
·三聚氰胺的缩合产物与多磷酸的转化产物，
·金属次膦酸盐，
·磷酸酯，
和/或其混合物。
5.根据权利要求1至4中任一项所述的流体输送管道，
其特征在于相对于模塑料的重量，所述外层分别包含5重量％至30重量％，优选10重量％至25重量％，特别优选11重量％至20重量％的至少一种阻燃剂。
6.根据权利要求1至5中任一项所述的流体输送管道，
其特征在于至少一种抗冲改性剂是官能化的抗冲改性剂，所述官能化的抗冲改性剂选自乙烯-丙烯共聚物、乙烯-1-丁烯共聚物、乙烯-丙烯-1-丁烯共聚物、苯乙烯共聚物、苯乙烯嵌段共聚物及其混合物。
7.根据权利要求1至6中任一项所述的流体输送管道，
其特征在于在所述内层中包含0.1重量％至30重量％，优选5重量％至25重量％，特别优选10重量％至20重量％的量的至少一种抗冲改性剂。
8.根据权利要求1至7中任一项所述的流体输送管道，
其特征在于所述外层包含选自以下的其他添加剂：
(i)0重量％至15重量％，优选2重量％至12重量％，特别优选4重量％至10重量％的至少一种增塑剂，
(ii)0.1重量％至2重量％，优选0.2重量％至1.5重量％，特别优选0.3重量％至1重量％的至少一种稳定剂，特别是热稳定剂，
(iii)0重量％至5重量％，优选0.1重量％至4重量％，特别优选0.2重量％至3.5重量％的选自UV稳定剂、导热添加剂、阻燃增效剂、加工助剂、润滑剂、着色和标记材料、无机颜料、有机颜料、IR吸收剂、膨胀剂、和/或其混合物的至少一种其他添加剂，
相对于模塑料的重量，所述添加剂(i)至(iii)的总和为0.1重量％至22重量％。
9.根据权利要求1至8中任一项所述的流体输送管道，
其特征在于，形成所述外层的模塑料具有根据ISO 307测量的1.6至1.9的相对黏度。
10.根据权利要求1至9中任一项所述的流体输送管道，
其特征在于形成所述外层的模塑料具有根据ISO 307测量的1.8至2.3的相对黏度。
11.根据权利要求1至10中任一项所述的流体输送管道，
其特征在于所述外层的厚度为0.1mm至1.5mm，优选为0.12mm至1.4mm，特别优选为0.15mm至1.3mm。
12.根据权利要求1至11中任一项所述的流体输送管道，
其特征在于所述流体输送管道在所述内层和所述外层之间没有黏合剂层，并且优选地由所述内层和所述外层组成。
13.根据权利要求1至12中任一项所述的流体输送管道，
其特征在于，所述流体为液体，优选为冷却剂，特别优选为水-醇混合物，特别是水-乙二醇混合物。
14.根据权利要求1至13中任一项所述的流体输送管道，
其特征在于所述流体输送管道为光滑管道或起伏管道的形式。
15.根据权利要求1至14中任一项所述的流体输送管道，
其特征在于流体输送管道是通过共挤出、吹塑和注塑，优选通过共挤出由用于所述内层和所述外层的模塑料能够制备的。
16.根据权利要求1至15中任一项所述的流体输送管道用于供应液体，优选水溶液，特别优选冷却剂，特别是水-醇混合物的用途。
17.根据权利要求16所述的用途，
其特征在于所述流体输送管道用于在电动机或电池中，特别是用于在电动车辆中供应流体。
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