CN1765623A - 多层树脂管 - Google Patents
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Abstract
一种多层树脂管包括多树脂层。至少最内树脂层由低渗透性树脂制成。该多层树脂管的至少一层树脂层是具有导电性并含导电长丝状填料的导电层。
Description
技术领域
本发明涉及一种用于汽车燃油管道的多层树脂管,更具体而言,涉及一种具有含碳纳米管导电树脂层的多层树脂管。
背景技术
汽车上的燃油管一般都一直采用金属管。为提高金属管的耐蚀性和耐化学性,金属管一般都镀有或涂有树脂膜。
最近,除了金属管以外还使用树脂管作燃油管道。树脂管有许多超过金属管的优点。树脂管不会生锈、容易加工、质轻且能提高设计自由度。
当燃油泵将燃油从燃油箱泵入汽车燃油管道以及当燃油流过汽车燃油管道时,由于燃油与燃油泵之间以及燃油与形成汽车燃油管道的燃油管之间的摩擦作用而产生静电并使燃油管带电。带电燃油管产生火花放电。火花放电损伤燃油管的涂膜,降低燃油管的耐蚀性和耐磨性。因此燃油管需要在车体上接地,以释放来自燃油管的静电。
由于树脂管本身是绝缘的,静电倾向于聚集在树脂管上,而聚集的静电容易引起麻烦。最近开发的导电管由含导电填料如炭黑或碳纤维的材料制成。由含导电填料的材料制成的传统导电树脂管的导电性随时间衰减,不能保持足够的导电性。
最近,要求拟用作燃油管的树脂管具有低渗透性,即阻止渗透的能力,以额外使燃油难以渗透过树脂管。从环保观点来看,低渗透性对防止燃油渗透过燃油管和燃油散发进大气是非常重要的。
术语“低渗透性树脂”用来表示满足由下文渗透性试验方法所确定质量的树脂。由SHED试验机进行的CARB DBL法是一种试验用于燃油管的树脂的代表性渗透性试验方法。
参考图6,试验一根内径为6mm、外径为8mm、长度等于或大于5m的树脂管2。将树脂管2的相对端通过密封接头5连接到一个由不锈钢制成的密闭容器4。将充满试验燃油的树脂管2在40℃保持50天或更长时间进行预处理。然后将该预处理过的树脂管2连接到图中未示出的SHED试验机上。SHED试验机测量渗透过树脂管2的和树脂管2中所含试验油内所含的烃量。当测得的烃量等于或低于50mg/m·天时,形成树脂管2的树脂就被称作低渗透性树脂。
设计上已满足所需低渗透性的传统多层树脂管具有要暴露于燃油的内层和覆盖内层且由粘合剂层粘结在内层上的外层,内层由低渗透性树脂制成,外层由聚酰胺或类似材料制成。但这种传统多层树脂管并不兼具导电性和低渗透性。
发明内容
因此本发明的目的是提供一种具有多层结构的多层树脂管,它包括由热塑性树脂制成的多树脂层,其中至少最内层是低渗透性树脂层,以及至少一层树脂层是由含导电长丝状填料的树脂制成的导电树脂层。
在本发明的多层树脂管中,优选填料是碳纳米管或碳长丝,其长度不短于根据对多层树脂管预期的伸长百分数和预期的工作长度所确定的最短长度。
在本发明的多层树脂管中,优选形成导电树脂层的树脂是聚苯硫醚树脂(PPS)、乙烯-四氟乙烯共聚物(ETFE)、聚酰胺11(PA11)或聚酰胺12(PA12).
即使导电树脂层的基体溶胀,导电树脂层的长丝状填料也不会断裂且导电树脂层能保持其导电性。所以这种多层树脂管能同时保持低渗透性和导电性。
附图说明
图1是本发明第一实施方案中多层树脂管的截面图;
图2是显示分散在基体中的碳纳米管的图;
图3是显示分散在基体中的碳长丝的图;
图4是本发明第二实施方案中多层树脂管的截面图;
图5是本发明第三实施方案中多层树脂管的截面图;和
图6是辅助说明树脂管防渗透能力试验法的示意图。
具体实施方式
下面将参考附图描述本发明优选实施方案中的多层树脂管。
第一实施方案
参考图1,即本发明第一实施方案中树脂管的截面图,该树脂管是具有三层树脂层的三层树脂管。这三层是第一层,即外层,第二层,即中间层,和第三层,即内层。要暴露于燃油的第三层,即内层,由具有低渗透性且含长丝状导电填料的热塑性树脂制成。因此该第三层兼具低渗透性和导电性。第一层不像第三层那样具有特别低的渗透性。形成第三层的热塑性树脂中所含的长丝状导电填料是碳纳米管或碳长丝。
表1给出了形成第一实施方案中多层树脂管第一层和第三层可能的树脂组合。
第一层,即外层,由聚酰胺树脂如PA11、PA12或PA6制成。优选第三层,即低渗透性层,由PPS或ETFE制成。优选在形成第三层的材料中,填料含量,即碳纳米管含量或碳长丝含量,为5~30重量%。当填料含量等于或低于5%时,多层树脂管的表面电阻率等于或低于105Ω/m。如果填料含量等于或高于30重量%,则第三层的拉伸强度和冲击强度过低。
如果第三层的低渗透性并不是一个重要的要求,则第三层的树脂可以是表1中所示组合5的PA11或组合6的PA12。
当低渗透性树脂含有碳纳米管时,分散在低渗透性树脂中的碳纳米管彼此缠结,如图2所示。当低渗透性树脂含碳长丝时,分散在低渗透性树脂中的碳长丝彼此缠结,如图3所示。
由于第三层含有导电填料,如碳纳米管或碳长丝,所以第一实施方案中的多层树脂管在用作汽车燃油管时发挥下述作用。
当多层树脂管用作汽车燃油管时,限定燃油通道的第三层将始终暴露在燃油中。那么,在形成第三层的树脂与燃油的羟基之间会发生氢键反应。随着氢键反应随时间的进行,第三层溶胀。如果第三层像传统多层树脂管中的内层那样含有炭黑或碳纤维,则炭黑颗粒之间或碳纤维之间的间隙就会膨胀并降低第三层的导电率。
如图2所示第三层中所含的碳纳米管或如图3所示第三层所含的碳长丝即使在作为基体的树脂溶胀时仍保持彼此缠结。因此第三层能保持其导电性。由于第三层由对燃油具有低渗透性的树脂制成,所以即使引起第三层溶胀,仍能保持其对燃油的低渗透性。因此第三层保持其原有的导电性和低渗透性。
碳纳米管或碳长丝的长度对保持第三层的导电性具有重要作用。树脂管要用在树脂管连续暴露于热的工作环境中。保持导电性所必需的碳纳米管或碳长丝的最小长度取决于尺寸变化,如伸长率。例如,用作汽车燃油管道的树脂管的长度最长为1000mm。假设1000mm树脂管的伸长率为0.3%。则树脂管的最大伸长量为3mm,因此当树脂管伸长时,分散在树脂中的碳纳米管或碳长丝可能会彼此分离,除非碳纳米管或碳长丝的长度等于或大于3mm。因此碳纳米管或碳长丝必需的最小长度是根据对树脂管预期的工作长度和对树脂管预期的伸长百分率决定的。
第二实施方案
本发明第二实施方案中的多层树指管有要暴露于燃油的第三层,即内层,由类似于第一实施方案中多层树脂管第三层的低渗透性树脂制成。第二实施方案中的多层树脂管与第一实施方案中多层树脂管的差别在于:前者的第一层,即外层,是由含导电长丝状填料的树脂制成的导电树脂层。
因此第二实施方案中多层树脂管的第一层和第三层分别是导电树脂层和低渗透性树脂层;即导电性和防渗透性分别赋予了第一层和第三层。由于分散在形成第一层的树脂中的碳纳米管或碳长丝增强了第一层并使第一层具有导电性,所以第一层提高了多层树脂管的冲击强度。
表2显示了形成第二实施方案多层树脂管中第一和第三层所可能的树脂组合。
第一层,即外层,由聚酰胺树脂如PA11、PA12或PA6制成。优选在形成第一层的材料中,碳纳米管或碳长丝的含量为5~30重量%。优选第三层即低渗透性层由PPS或ETFE制成。
第三实施方案
参考图5,即本发明第三实施方案中多层树脂管的截面图,该第三实施方案中的多层树脂管是第一实施方案中的多层树脂管和第二实施方案中的多层树脂管各自构型的选择性组合。第三实施方案中的多层树脂管具有第一层,即外层,和要暴露于燃油的第三层,即内层。第三层由低渗透性树脂制成。第一层和第三层分别都由含导电长丝状填料的树脂制成。
与第一实施方案中的多层树脂管类似,第三实施方案中的多层树脂管具有提高的导电性。导电长丝状填料,即碳纳米管或碳长丝,提高了多层树脂管的强度。
表3给出了形成第三实施方案多层树脂管中第一和第三层所可能的树脂组合。
表1
1 | 2 | 3 | 4 | 5 | 6 | |
第一层 | PA | PA | PA | PA | PA | PA |
第三层导电填料 | PPSCNT | ETFE碳长丝 | ETFECNT | PPS碳长丝 | PACNT | PA碳长丝 |
表2
1 | 2 | 3 | 4 | 5 | 6 | |
第一层 | PA | PA | PA | PA | PA | PA |
导电填料 | CNT | 碳长丝 | CNT | 碳长丝 | CNT | 碳长丝 |
第三层 | PPS | ETFE | ETFE | PPS | PA | PA |
表3
1 | 2 | 3 | 4 | 5 | 6 | |
第一层 | PA | PA | PA | PA | PA | PA |
导电填料 | CNT | 碳长丝 | CNT | 碳长丝 | CNT | 碳长丝 |
第三层 | PPS | ETFE | ETFE | PPS | PA | PA |
导电填料 | CNT | 碳长丝 | CNT | 碳长丝 | CNT | 碳长丝 |
Claims (12)
1.一种具有多层结构的多层树脂管,包含由热塑性树脂制成的多树脂层,
其中至少最内层是低渗透性树脂层,并且至少一层树脂层是由含导电长丝状填料的树脂制成的导电树脂层。
2.按照权利要求1的多层树脂管,其中导电长丝状填料单元的长度不短于根据对多层树脂管预期的伸长百分率和预期的工作长度所决定的最短长度。
3.按照权利要求2的多层树脂管,其中导电长丝状填料单元的长度大于预期伸长百分率和预期工作长度的乘积。
4.按照权利要求1的多层树脂管,其中低渗透性树脂层还起导电层作用。
5.按照权利要求1的多层树脂管,其中导电树脂层由聚苯硫醚树脂、乙烯-四氟乙烯共聚物、聚酰胺11或聚酰胺12制成。
6.按照权利要求1的多层树脂管,其中导电填料单元是碳长丝。
7.按照权利要求1的多层树脂管,其中导电填料单元是碳纳米管。
8.按照权利要求6的多层树脂管,包括含碳长丝的单层或含碳长丝的多层。
9.按照权利要求7的多层树脂管,包括含碳纳米管的单层或含碳纳米管的多层。
10.按照权利要求6的多层树脂管,其中导电树脂层含5~30重量%碳长丝。
11.按照权利要求7的多层树脂管,其中导电树脂层含5~30重量%碳纳米管。
12.按照权利要求1的拟用作汽车燃油管的多层树脂管。
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US7111646B2 (en) | 2006-09-26 |
JP2006118670A (ja) | 2006-05-11 |
EP1650018A1 (en) | 2006-04-26 |
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US20060086402A1 (en) | 2006-04-27 |
CN100360307C (zh) | 2008-01-09 |
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