CN113833912A - 多层管的组成和制造方法 - Google Patents

多层管的组成和制造方法 Download PDF

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CN113833912A
CN113833912A CN202110691133.8A CN202110691133A CN113833912A CN 113833912 A CN113833912 A CN 113833912A CN 202110691133 A CN202110691133 A CN 202110691133A CN 113833912 A CN113833912 A CN 113833912A
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layer
polypropylene
tube
multilayer tube
thermoplastic material
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聂涛
Y·张
D·A·本斯科
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Cooper Standard Automotive Inc
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Cooper Standard Automotive Inc
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Abstract

本公开包括多层管，所述多层管包括包含热塑性材料的内层、包含高密度聚乙烯(HDPE)的中间层；以及包含热塑性材料的外层。HDPE中间层夹在热塑性材料的外层和内层之间。选择热塑性材料以促进挤出并为任何低温乙二醇冷却系统应用提供低成本、坚固的多层管。

Description

多层管的组成和制造方法
技术领域
本公开涉及一种用于机动车辆中的管。更具体地，本公开涉及一种多层管，其可用于运输流体以在机动车辆中进行温度控制。
背景技术
已经提出将诸如塑料和弹性体的合成材料的单层和多层管用于冷却剂管线。电动汽车的冷却剂管线需求不断增长。电动汽车和内燃机汽车的冷却系统类似。两者都通过一系列热交换管循环冷却剂，以将热量从发动机中转移出去。
电动车辆中的电池必须与机动车辆的其他常规部件一起冷却。电动汽车电池的冷却系统在最多约60℃的温度下运行，这明显低于内燃机冷却系统运行的温度(最多约125℃)。电动汽车运行的较低温度为使用不同的冷却管材料提供了机会。
重要的是，冷却剂管由提供防止冷却剂扩散和泄漏的屏障的材料构成。此外，由于管子将在低温下携带冷却剂，因此它必须能够承受冷砾石冲击而不会在低温下破裂。此外，冷却剂可能会在冷却系统中以较高的压力传输，因此管子必须具有足够的爆破压力和连接或环向强度，以便通常使用带倒钩的快速连接器连接到系统。
一般而言，最成功的多层管已经采用由耐外部环境的材料构成的外层共挤出。最内层由能够阻止冷却剂扩散、低成本和长期适用性的材料组成。
由于高密度聚乙烯(HDPE)在内燃机中的冷却剂系统中预期暴露于接近其熔点的温度，因此先前认为将高密度聚乙烯(HDPE)用于冷却剂管是不实用的。然而，电池供电和混合动力电动汽车中的冷却系统为具有出色耐冷却剂性且成本低于市场上其他材料的材料提供了新的广泛机会。
一个目的是提供一种低成本的多层管，其将在机动车辆中，特别是在电动机动车辆中例外地输送流体。
发明内容
本公开包括多层管，该多层管包括包含热塑性材料的内层、包含高密度聚乙烯(HDPE)的中间层和包含热塑性材料的外层。HDPE是一种低成本材料，具有很好的耐冷冲击性。HDPE中间层夹在热塑性材料的外层和内层之间。选择热塑性材料以促进低成本、坚固多层管的平衡管材特性，例如密封性、爆裂强度、连接器环向强度和易于挤出。
附图简述
下面结合附图对本发明的一个或多个示例性实施方案进行说明，其中:
图1是根据本公开的具有三层的管的平面图；
图2是穿过图1的管的截面图；
图3是穿过图2的管的一个替代实施方案的截面图；
图4是穿过图2的管的另一个替代实施方案的截面图；
图5是穿过图2的管的另一实施方案的截面图；
图6是穿过图4的管的又一个实施方案的截面图；
图7是穿过图4的管的另一替代实施方案的截面图；和
图8是制造本公开的管的过程的示意图。
具体实施方式
本公开是图1和图2所示的多层管10。管10具有至少一个内层或第一层14、至少一个中间层或第二层16以及至少一个第三层或外层18。管10优选地通过在传统共挤工艺中同时共挤出热塑性材料来制造。管10可以被共挤出到合适的长度，或者可以以连续的长度共挤出并随后切割以适合给定的应用。本公开的管10可具有高达约50mm的外径和约5mm至约30mm的内径。总壁厚可以为0.9至约7mm，合适地为约1至约3mm，并且优选地为1至约2mm。管也可以具有光滑的孔或波纹表面。
管10可用于电动车辆中的电池的冷却剂输送以及电动和内燃车辆中的发动机的低温冷却剂输送。通常，冷却剂将是某种类型的乙二醇基冷却剂，例如乙二醇。对于电池或发动机冷却应用，管10通常会遇到约60℃至约70℃的连续温度和约80至约95℃的峰值温度和约1至4巴的最大表压。
管10包括聚乙烯中间层16。优选地，中间层是HDPE。HDPE以其高强度/密度比而闻名。HDPE具有优异的耐低温冲击性。HDPE的密度可以在930至970kg/m3的范围内，优选为940至950kg/m3。HDPE几乎没有支化，因此比低密度聚乙烯具有更高的密度和更强的分子间力和拉伸强度。乙烯单体可以在适当的聚合条件下用齐格勒-纳塔催化剂聚合以产生HDPE。使用ISO 8256测试，HDPE在-30℃下应具有约95至约105KJ/m2的冷拉伸冲击强度。HDPE具有相对较低的环向强度。因此，中间层中的HDPE夹在内层14和外层18之间以提供必要的质量。中间层16可具有约0.1至约1mm，优选约0.1至约0.7mm的壁厚。在本文公开的任何实施方案中，管10可包括通过涂覆中间层的内表面而围绕中间层16的内层14。管10还可包括外层18，其通过涂覆中间层的外表面而围绕中间层16。中间层16可以完全包裹在内层14和外层18之间。
内层14可以在挤出过程中与其他层共挤出，或者其他层可以在随后的过程中围绕内层挤出，例如通过十字头挤出。外层18可以在挤出过程中与其他层共挤出，或者可以在随后的过程中围绕其他层挤出，例如通过十字头挤出。内层14可以包括根据其抗冷却剂渗透性、柔韧性、连接密封能力、环向强度和绝缘特性而选择的材料，并且可以具有约0.1至约1mm，优选地约0.1至约0.7mm的壁厚。外层18可以包括根据其结构特性(例如耐磨性、环向强度、抗冲击性、耐化学性或绝缘特性)，其可挤出性和光洁度选择的材料并且可以具有约0.1至约1mm，优选地约0.1至约0.8mm的壁厚。
在一个实施方案中，内层14和外层18可以由可熔融加工的热塑性材料制成。内层14和外层可以由相同或不同的热塑性材料制成。热塑性材料可以是选自具有不超过四个碳原子的取代或未取代烯烃的均聚物或共聚物、乙烯醇或乙酸乙烯酯、以及它们的混合物的热塑性材料。热塑性材料可以选自耐氯化锌的尼龙6、尼龙11、尼龙12、聚醚嵌段酰胺。
用于内层和/或外层18的优选热塑性材料包括聚丙烯。聚丙烯可以是聚丙烯均聚物、聚丙烯共聚物或聚丙烯基热塑性弹性体(TPE)。聚丙烯共聚物包含与至少另一种烯烃单体聚合的丙烯。在共聚物中，聚丙烯与聚合物链中的其他烯烃单体共价键合。聚丙烯均聚物或共聚物可以通过任何已知的方法制造。例如，丙烯聚合物可以在齐格勒-纳塔催化剂体系或茂金属催化剂体系存在下由丙烯单体制备。可以类似地制造嵌段共聚物，不同的是丙烯通常首先在第一反应器阶段中单独聚合或与另一种烯烃单体聚合以形成半结晶基质，然后在第二阶段或后续阶段中在第一反应器中产生的聚合物存在下丙烯的低结晶度或无定形链段和其他烯烃单体共聚。所述其他烯烃单体应具有不超过四个碳原子，优选乙烯。商业聚丙烯无规和嵌段共聚物可从多个聚丙烯生产商处广泛获得，包括各种等级。优选无规聚丙烯共聚物。
丙烯的无规共聚物可包含以无规方式插入的共聚单体，从而破坏主链结晶度，导致共聚物的熔点从均聚丙烯的约165℃降至无规共聚丙烯中的低至约130℃，取决于所用共聚单体的数量和类型。
聚丙烯的共聚物可以在多步方法中共聚以获得嵌段共聚丙烯，其中链段由相对结晶的均聚丙烯或无规共聚丙烯和相对无定形或低结晶度的丙烯乙烯共聚物的链段组成。嵌段共聚物的熔点将由共聚物的结晶度更高的链段支配，以给出均聚丙烯嵌段共聚物的约165℃或无规共聚丙烯嵌段共聚物的更低的熔点。
乙烯是聚丙烯共聚物的优选共聚单体，但其他烯烃单体可能是合适的。此外，无规共聚丙烯优于嵌段共聚丙烯。丙烯共聚物中共聚单体，特别是乙烯的质量分数应该在约0.1和约15重量％之间，优选在约0.2和约6重量％之间。
用于内层和/或外层18的另一种优选的热塑性材料是TPE。TPE是一种包括主相和弹性体或橡胶第二相的热塑性材料。热塑性弹性体具有热塑性材料的特性，但硬度更像橡胶。粘附到聚乙烯中间层16的合适的TPE是最合适的。合适的热塑性弹性体包括热塑性橡胶，其具有由苯乙烯-乙烯/丁烯-苯乙烯嵌段共聚物和带有增塑剂的聚氯乙烯复合物构成的组成。
优选的TPE是热塑性硫化橡胶(TPV)。TPV是一种大部分完全固化的乙烯-丙烯二烯单体(EPDM)颗粒封装在聚丙烯基质中的硫化合金。聚丙烯基质构成主相，乙烯-丙烯二烯单体构成第二相。TPV可从各种供应商处商购获得，包括在SANTOPRENE产品线下，一种热塑性橡胶组合物，来自ExxonMobil Chemical，Irving，Texas和SARLINK产品线，一种耐油热塑性组合物，可从Teknor Apex of Pawtucket,Rhode Island商购获得。TPV也可从ElastronGroup获得，其在Kocaeli,Turkey制造。基于ISO 868，优选的TPV应具有约55至约95，优选地约80至约90的肖氏A硬度。不具有EPDM相的热塑性材料，例如聚丙烯将具有更大的肖氏A硬度。如果需要，可以对这些材料进行改性以包括阻燃剂、增塑剂等。
为了在包含聚丙烯的层和包含聚乙烯的层之间获得强粘合，可以使用粘合层。如图3所示，管20可以具有介于中间层16和外层18之间的粘合层22。我们已经发现TPE的外层18，特别是TPV，不需要粘合层22并且可以直接粘合到HDPE的中间层16上，如图2所示。
如图4所示，管30具有介于中间层16和内层14之间的粘合层32，并且内层包括热塑性材料，例如聚丙烯。我们已经发现TPE的内层14，特别是TPV，不需要粘合层32并且可以直接粘合到HDPE的中间层16上，如图2所示。如图5所示，管40具有介于中间层16和内层14之间的第一粘合层42和介于中间层16和外层18之间的第二粘合层44，因为内层和外层包括热塑性材料，例如聚丙烯，它不是TPE，尤其不是TPV。在一个实施方案中，具有聚丙烯主相和EPDM第二相的TPV与HDPE中间层16结合良好。
当管10、20、30或40不会遭受长时间升高的温度时，可以采用乙烯共聚物基粘合剂作为粘合层22、32、42或44，例如乙烯乙酸乙烯酯和乙烯丙烯酸甲酯粘合剂。低密度乙烯-α-烯烃共聚物或更高共聚单体丙烯-α-烯烃共聚物基粘合剂也可用作粘合层22、32、42或44。
用于粘合层22、32、42或44的合适粘合剂可以是聚丙烯基粘合剂或TPE基粘合剂。优选的聚丙烯基粘合剂是酸酐改性的聚丙烯树脂。每个粘合层22、32、42或44可具有约0.05至约0.5mm，优选约0.05至约0.2mm的壁厚。
图6示出了本公开的管50的实施方案，其包括包含外部层56的外护套。管50可以采用本文的实施方案中的任一个，但图6使用图4的实施方案作为代表。外部层56围绕外层18并且可以包括不同于外层的热塑性材料的热塑性材料。当外层18是诸如聚丙烯的热塑性材料时，外部层56可以是诸如TPV的热塑性弹性体。当外层18是诸如TPV的热塑性弹性体时，外部层56可以是诸如聚丙烯的热塑性材料。
图7示出了本公开的管60的实施方案，其包括包含内部层68的内管。管60可以采用本文的实施方案中的任一个，但图7使用图4的实施方案作为代表。内层14围绕内部层68，并且内部层可以包括不同于内层的热塑性材料的热塑性材料。当内层14是诸如聚丙烯的热塑性材料时，内部层68可以是诸如TPV的热塑性弹性体。当内层14是诸如TPV的热塑性弹性体时，内部层68可以是诸如聚丙烯的热塑性材料。
虽然制备具有多个各种热塑性材料覆盖层的管材在本公开的范围内，但本公开的管10、20、30、40、50、60通常具有最大九层，包括粘合层。在优选实施方案中，管10、20、30、40、50、60具有三层或四层。
本发明的管10、20、30、40、50、60适用于机动车辆，并且可以包括外层18或外部层56，其与外部环境不发生反应并且可以承受各种冲击、振动疲劳和温度变化，以及暴露在各种腐蚀性或降解化合物中，在机动车辆的正常运行过程中会暴露于这些化合物中。适用于本发明的材料可由任何可熔融加工的可挤出热塑性材料组成，这些材料可抵抗紫外线降解和热的极端变化。选择的材料还可以表现出对环境危害的抵抗力，例如暴露于道路盐、氯化锌和CaCl2，以及在与发动机油和制动液等材料接触时抵抗降解。
现在参考图8，示出了生产本公开的管10、20、30、40、50、60的方法的示意图100。该方法包括至少同时挤出包含热塑性材料的内层14、围绕内层的包含HDPE的中间层16和围绕中间层的包含热塑性材料的外层18的步骤。挤出通过挤出机102进行，所述挤出机用于将聚合物材料挤出成合适的管状结构，该结构至少包括内层14、中间层16和外层18。一个或更少的挤出机102、104、106、108和/或110可用于要挤出的每一层。一个或多个粘合层也可以在中间层16和包含热塑性材料例如丙烯的内层14和/或外层18之间挤出。应当理解，可以根据需要使用更少或任意数量的挤出机。如果使用多于一台的挤出机，则材料然后通过共挤出头112。然后该方法包括通过例如水箱114进行骤冷的步骤。共挤出管10、20、30、40、50或60然后通过拉拔器116送出，之后通过切割器122将管切割成所需长度。
多层管10、20、30、40、50、60具有汽车冷却剂运输所需的强特性。管10、20、30、40、50、60预计可在-40℃下承受1.5J(2ft-lbs)的冲击力，并且表现出比传统EPDM管更好的抗冷却剂渗透性。管10、20、30、40、50、60能够制成波纹管而不会分层，并且具有足够的抵抗在典型操作期间将遇到的爆裂压力的能力，并且还能够承受在制造和测试过程中将遇到的真空压力。该管还具有足够的密封能力和环向强度，使其能够与带倒钩的连接(barbedconnection)结合而不会泄漏。
虽然以下结合具体实施方案进行描述，但是应当理解，该描述旨在说明而不是限制前述描述和所附权利要求的范围。
无需进一步详述，相信利用前述描述，本领域技术人员可以最大限度地利用本发明，并容易地确定本发明的基本特征，在不脱离本发明的精神和范围的情况下，对本发明进行各种改变和修改，使其适应各种用途和条件。因此，前述优选的具体实施方案应被解释为仅是说明性的，而不以任何方式限制本公开的其余部分，并且旨在涵盖包括在所附权利要求的范围内的各种修改和等效布置。
在上文中，除非另有说明，否则所有温度均以摄氏度表示，并且所有份数和百分比均以重量计。

Claims (21)

1.一种多层管，包括：
包含热塑性材料的内层；
包含高密度聚乙烯的中间层；和
包含热塑性材料的外层。
2.根据权利要求1所述的多层管，其中所述内层包含聚丙烯。
3.根据权利要求2所述的多层管，其中所述内层包含聚丙烯共聚物。
4.根据权利要求2所述的多层管，还包括在所述内层内侧的内部层，其包含热塑性材料。
5.根据权利要求1所述的多层管，还包括位于中间层和内层之间的粘合层。
6.根据权利要求1所述的多层管，其中所述内层包含热塑性弹性体。
7.根据权利要求6所述的多层管，其中所述内层包含热塑性硫化橡胶。
8.根据权利要求7所述的多层管，其中所述内层直接粘合到所述中间层。
9.根据权利要求1所述的多层管，其中所述外层包含聚丙烯。
10.根据权利要求9所述的多层管，其中所述外层包含聚丙烯共聚物。
11.根据权利要求9所述的多层管，还包括位于所述外层外侧的外部层，其包含热塑性弹性体。
12.根据权利要求10所述的多层管，还包括在中间层和外层之间的粘合层。
13.根据权利要求1所述的多层管，其中所述外层包含热塑性弹性体。
14.根据权利要求13所述的多层管，其中所述外层包含热塑性硫化橡胶。
15.根据权利要求14所述的多层管，其中所述外层直接粘合到所述中间层。
16.一种多层管，包括：
包含聚丙烯或热塑性弹性体的内层；
包含高密度聚乙烯的中间层；和
包含聚丙烯或热塑性弹性体的外层。
17.根据权利要求16所述的多层管，其中所述内层和所述外层中的至少一个包含聚丙烯共聚物。
18.根据权利要求16所述的多层管，其中所述内层和所述外层中的一个包含聚丙烯，并且还包括位于中间层和包含聚丙烯的层之间的粘合层。
19.根据权利要求16所述的多层管，其中所述内层和所述外层中的至少一个包含热塑性硫化橡胶。
20.一种制造多层管的方法，包括：
挤出包含热塑性材料的内层、围绕所述内层的包含高密度聚乙烯的中间层、和围绕所述中间层的包含热塑性材料的外层；其中所有层是同时挤出的。
21.根据权利要求20所述的方法，还包括同时挤出在中间层与包含聚丙烯的内层和外层中的至少一个之间的粘合层。
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