CN102883882A - 高温绝缘带和用其覆套的电线或电缆 - Google Patents
高温绝缘带和用其覆套的电线或电缆 Download PDFInfo
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Abstract
本发明提供复合绝缘带(20)，其包括具有至少两层的叠层物或共挤出物，所述叠层物或共挤出物包括具有分散有云母粒子的聚合物基质的绝缘第一层(24)和具有含有芳族环和/或杂环且具有至少350℃的熔点和至少150℃的玻璃化转变温度的聚合物的第二层(26)。所述带可用以在诸如电线的导体(10)上形成多层包覆层。具有诸如PTFE的含氟聚合物的外部保护层(28)可通过包裹或挤出围绕所包裹的带而施加。
Description
本发明涉及适合在诸如在钻井或采矿、商用或军用航空航天和船舶应用及汽车、轨道和大量运输的有需求的或恶劣的条件中使用的高性能、耐高温的电线和电缆，其还可为耐火的。这类电缆可能暴露于极端温度以及暴露于腐蚀性物质或气氛或者暴露于火。高性能电线通常包括功能性芯，诸如电导体或光学纤维；和一个或多个绝缘和/或保护包覆层。这些包覆层应为柔性且体积不庞大的，因为在很多情况下需要电线具有小直径。所述小直径、高性能的电线可通过包裹薄的单层或多层带、通过挤出或通过这些技术的组合来形成。
已知各种类型的聚合物适用于电线和电缆护套，诸如聚四氟乙烯(PTFE)和聚醚醚酮(PEEK)。PTFE具有非常坚韧以及化学惰性、高软化点、低摩擦系数和优良电绝缘性质的优势。已经发现PEEK日益用于电线和电缆护套中，因为其具有优良的耐燃性、在极低发烟的情况下自动灭火。其还具有优良伸长率、处于诸如薄膜的薄片状态下的优良柔性和对于动态切割和擦刮磨损的优良机械抗性。然而，其可对电弧径迹以及由丙酮和强酸引起的侵蚀敏感。
EP-A-572 177公开了多孔PTFE和PEEK的电绝缘叠层物。其目的在于提供用于航空电线绝缘的柔性电绝缘材料，其为轻质的，具有高机械强度、耐热性和耐化学性及降低的介电常数。
需要耐火以及耐极高温度的电线和电缆绝缘材料。赋予这种耐燃性的一种方式是施加包含分散在聚合物基质中的云母粒子(典型地薄片)的包覆层。JP-A-2003100149例如公开了细云母粉和玻璃粉在聚硅氧烷树脂中的分散体用于涂覆耐火电缆的用途。
然而，云母可增加成本且因此需要降低电缆护套的云母含量。例如，JP-A-2006120456设法通过组合玻璃带以赋予聚硅氧烷带拉伸强度和尺寸稳定性来赋予耐热性、电特性和胶粘性来避免使用云母。
JP-A-2000011772公开了用与氢氧化铝和云母粉混合的交联聚硅氧烷橡胶制成的耐火包覆层。还需要直径减小的电线和电缆，其可通过使用厚度减小的护套来获得。
GB-A-2460686公开了具有功能性芯和包括包含分配在诸如聚硅氧烷的聚合物基质中的云母粒子的内部防火层、PEEK包裹薄膜和具有PEEK或另一聚合物的外包覆层的护套的电线。以这种方式，可得到需要的耐温度性和耐燃性，而云母限制在三层中的一层中，该层的厚度优选不超过100μm。
WO8900757 (Penneck)描述了具有优良电性质和机械性质的电线，其具有围绕导体的无机电弧控制层、围绕电弧控制层的包含芳族聚合物的绝缘层和围绕绝缘层的第二径迹控制层。该电线显示出优良的耐干电弧和湿径迹性质。
然而，仍然需要除了具有优良的绝缘性和耐高温性以外还具有特别是在高温下改善的机械性质的电线和电缆。
根据本发明的第一方面，提供包括具有至少两层的叠层物或共挤出物的复合绝缘带，所述叠层物或共挤出物包括具有聚合物基质的绝缘第一层，其优选耐高温且也可耐火，其中分散有云母粒子；和具有含有芳族环和/或杂环且具有至少350℃的熔点和至少150℃的玻璃化转变温度的聚合物的第二构造层。
绝缘云母层可具有背衬层，例如具有玻璃纤维的支撑层或具有诸如聚烯烃的另一聚合物的层。
在另一实施方案中，复合带可具有施加到第二层的与第一层相反的表面上和/或施加到第一层的与第二层相反的表面上的含氟聚合物包覆层。所述含氟聚合物层可例如基于PTFE、PFA或FEP且可通过包括施加为包覆层的各种方法施加。
施加到电线的内部和/或外部含氟聚合物层的优势包括：
(i) 增强的电绝缘；
(ii) 改善的对于电线终端的绝缘材料剥落；和
(iii) 在含氟聚合物包覆层在用包裹的带绝缘的电线外侧的情况下，可以加热该含氟聚合物层以将其熔化并产生均匀层。
根据本发明的另一方面，提供包括芯和聚合物护套的电线或电缆，其中所述护套包括：
(a) 用靠近所述芯的第一层包裹于所述芯周围的如上定义的复合绝缘带；和
(b) 包裹的或挤出的具有含氟聚合物的外层。
绝缘第一层包含分散在诸如聚合硅氧烷的聚合物基质中的云母。
可以有利地在施加挤出的外部含氟聚合物层之前施加胶粘连接层，特别是在复合带包括含氟聚合物包覆层且在包裹带的第二层上形成外包覆层的情况下。所述连接层的合适材料包括用环氧化物或顺丁烯二酸官能化的(epoxy or maleic functionalized)氟化弹性体或更优选诸如PFA或PTFE的官能化含氟聚合物。所述胶粘连接层可通过挤出或通过诸如浸涂的其他涂覆方法施加。
另外或供选地，可在施加含氟聚合物外层之前进行加热或烧结步骤以熔化包裹的复合带的第一层和第二层。
为了额外的强度、耐化学性、柔性和/或耐燃性而提供含氟聚合物外层(b)。该外层例如可包含聚四氟乙烯(PTFE)、聚偏氟乙烯(PVDF)、聚乙烯四氟乙烯(ETFE)、聚氟烷氧基(PFA)或这些聚合物的任意的共聚物或共混物或合金。该外层可固定或可优选在350℃-420℃的温度下熔化或烧结。
带的第二构造层例如可包含聚芳醚酮(PAEK)或其共混物或合金。这些包含芳族环的链，其中一些芳族环由氧原子连接，且其他芳族环由羰基连接。适合本发明的目的的那些具有比PEEK高的熔点和玻璃化转变温度。
具有所需要的熔点(Tm)和玻璃化转变温度(Tg)的PAEK的实例列于下表1中，其中所述聚合物由其缩写名称识别，其中E代表醚，K代表酮且Φ指代苯环，因此例如PEKK为聚醚酮酮。优选的聚合物为其中酮连接键与醚连接键的比例为1:1或更大的那些聚合物，这些化合物具有较高的Tg和Tm。
。
第二层可具有25-100μm、更优选25-75μm的厚度。在一些实施方案中，带的第一层和第二层(a)和外部含氟聚合物层(b)各自具有25-50μm的厚度。
第二层可包含含有至少50%且更优选65%的PAEK的共混物或合金。对于需要高度阻燃性的电线和电缆，将需要特别是含云母的聚合物的较厚层。在使用时，内部含氟聚合物包覆层和外部含氟聚合物包覆层将优选具有2-25μm的厚度。
可与PAEK共混或合金化的聚合物包括由含有与五元环稠合的六元环的杂环单元构成的那些聚合物，例如聚酰亚胺、聚苯并咪唑、聚苯并噁唑和聚苯并噻唑和其共聚物。
上述带可施加到许多不同类型的芯，尤其是导线或电缆，例如铜，其可为镀镍或镀锡或镀银的；铝，通常为包铜铝；银或钢。出于其他目的，可使用非金属芯，诸如碳纤维或聚合物芯或陶瓷芯。电缆可为单芯或多芯的或可包括双绞线电线、多股芯或编带。这些芯中的任一个可用铜、镍、锡或银涂覆。
现将参考附图描述本发明的优选的实施方案，其中：
图1显示根据本发明的绝缘电线可如何通过包裹含有PAEK和其他聚合物的复合带来制成；
图2为根据本发明的第一实施方案的多层包覆的电线的截面图；
图3为根据本发明的第二实施方案的包覆的电线的截面图；及
图4为根据本发明的另一实施方案的复合带的放大图。
首先参看图1，多股导线10具有通过卷绕和挤出对其施加的三层护套，所述多股导线10可例如由以下材料制成：未涂覆或用镍、银或锡涂覆的铜；铝，其可为包铜的；钢或非金属电缆，诸如碳纤维、聚合物纤维或陶瓷纤维。复合带20螺旋卷绕到芯上以形成卷绕包覆层16。
复合带包括例如具有分配在其中的云母薄片的聚硅氧烷的第一层24。最靠近芯10的表面包括具有诸如PTFE的含氟聚合物的包覆层25。
在第一层24的相反侧上叠层有具有例如聚芳醚酮的第二层26。
最后，具有含氟聚合物的外层28例如通过挤出或带包裹来施加。在图1中，该层显示为挤出的，但其也可作为具有第一层24和第二层26的复合薄膜包裹。
第一层和所述第二层优选以40-70%、优选48-58%的重叠螺旋卷绕于芯周围。
图2显示电缆的截面图，其已经绕导体10施加三层护套，所述导体10例如对照图1而描述。直接围绕导体的第一层24为含云母的护套以赋予绝缘性和可能的耐燃性。其例如可由含云母的聚硅氧烷制成。该层可在其内表面上紧挨着导体具有PTFE或聚硅氧烷的包覆层25。或者，云母层的该侧可用玻璃纤维和/或聚乙烯层背衬。
第二层26包含聚芳醚酮，其厚度为25-100μm。PAEK可单独使用或作为与其他聚合物的共混物或合金使用。所述共混物或合金将优选含有至少50%且更优选至少65%的PAEK。
外层28可作为具有第一层和第二层的复合带的一部分合适地挤出或包裹。其提供封装层以形成对电缆的额外防护层。可使用上文对于该层所列出的聚合物、聚合物共混物或合金中的任一种。例如，可根据航空航天市场需要将PTFE烧结以提供卓越的耐化学性。
在该实施方案中含云母的聚合物与PAEK的协同组合可提供具有可能的低重量和小总直径的耐高温耐火电线。云母可提供绝缘性和至高1000℃的耐火性，且与PAEK组合提供改善的机械性质，包括耐动态切割性，甚至是在高温下；不燃烧特性和极低的冒烟性。可包括高温烧结的制造方法必须支持在构造PAEK层中的半结晶性。
两层24和26如在图1中那样地施加为预成型的单一复合包裹层，其可由在具有所需要的高Tm值和Tg值的具有芳族聚合物的薄膜或带上的单或双云母层形成。所述云母层包含分配在诸如聚硅氧烷或聚合硅氧烷的聚合物基质中的云母粒子，其具有或不具有内包覆层25。对于外部含氟聚合物层28，含量的范围可与在上述实施方案中相同。此外，可将该外层烧结。
如在图3中所说明，包裹的复合薄膜36可作为用于各种电线或电缆构造的构造层使用。这可包括具有另一聚合绝缘材料的导体、具有或不具有编带的完整电缆构造，诸如双绞线或四心双绞线(quad of twisted pairs)，诸如Cat 7电缆。在图3中说明的实施方案中，本发明的三层包覆层围绕三芯电缆30用在氧化硅等基质中的云母粒子的内部防火或耐火绝缘层32、PAEK或另一芳族和/或杂环聚合物或聚合物共混物的中间层34和外部保护层38形成，外部保护层38可具有选自与上述实施方案的保护层相同范围的组成。
为了使得保护性护套更坚韧和更耐化学侵蚀，围绕本发明的电线或电缆的护套可通过电子束辐射、优选在高温下且优选在惰性气氛中交联。
最后，所述护套可经受合适地在170-300℃下、优选至少12小时且多达24小时的退火处理。
现参看图4，描述根据本发明的另一实施方案的复合材料表，其中第一层和第二层分别编号为44和46。这些层可具有与在图1-3的实施方案中的相应层相同的组成。
在该实施方案中，氟烃包覆层45施加到第一层的与第二层相反的一侧上，其将在有待通过围绕导体包裹带来形成的包覆层的内侧。第二氟烃包覆层47在第一包覆层44的相反侧施加到第二包覆层46上。这将因此构成包裹薄膜的外层，具有含氟聚合物的另一保护性外层可通过包裹或挤出施加于其上。
本发明的复合带优选在设计上模块化。可使云母层的厚度增加以在电绝缘之外赋予成比例地增强的耐火性质。虽然该层的优选厚度对于大多数场合不会超过50μm，以保持电线总直径最小，但当要求耐火性时，该层的厚度可大于50μm，例如在50-100μm范围内。还可调节其他层的厚度以满足个别需求。
Claims (18)
1.复合绝缘带(20)，其包括具有至少两层的叠层物或共挤出物，所述叠层物或共挤出物包括具有分散有云母粒子的聚合物基质的绝缘第一层(24)和具有含有芳族环和/或杂环且具有至少350℃的熔点和至少150℃的玻璃化转变温度的聚合物的第二层(26)。
2.权利要求1的复合绝缘带，其中所述第二层(26)包含含有至少65重量%的聚芳醚酮(PAEK)的共混物或合金，所述聚芳醚酮具有至少1:1的酮与连接芳族环的醚基的比例。
3.权利要求2的复合绝缘带，其中所述第二层(26)的PAEK与含有与五元环稠合的六元环的杂环单元的聚合物共混或合金化。
4.前述权利要求中任一项的复合绝缘带，其中所述绝缘第一层(24)具有施加到其与所述第二层(26)相反的表面上的氟烃或聚硅氧烷层或包覆层(25)。
5.前述权利要求中任一项的复合绝缘带，其还包括在所述第二层(46)的与所述第一层(44)相反的一侧上的具有含氟聚合物的层(47)。
6.电线或电缆，其包括芯(10)和聚合物护套(16、28)，其中所述护套包括：
(a) 用靠近所述芯的所述第一层(24)包裹于所述芯周围的前述权利要求中任一项的复合绝缘带(20)和
(b) 包裹的或挤出的具有含氟聚合物的外层(28)。
7.权利要求6的电线或电缆，其中所述外部保护性聚合物层(28)烧结或熔化。
8.权利要求6或7的电线或电缆，其中所述第二层(26)至少部分地烧结或熔化。
9.权利要求8的电线或电缆，其中所述整个护套(16)烧结。
10.权利要求6-9中任一项的电线或电缆，其中所述叠层复合薄膜(20)以40-70%、优选48-58%的重叠螺旋卷绕到所述芯(10)上。
11.权利要求6-10中任一项的电线或电缆，其中所述保护性外层作为所述复合带的层卷绕于所述芯周围。
12.权利要求6-10中任一项的电线或电缆，其中所述外部保护层(28)通过挤出形成。
13.权利要求6-12中任一项的电线或电缆，其中所述第一层(24)和所述第二层(26)和所述保护性外层各自具有25-100μm的厚度。
14.权利要求6-12的电线或电缆，其中所述第一层(24)和所述第二层(26)和所述保护性外层(28)各自具有25-50μm的厚度。
15.制造绝缘电线或电缆的方法，其包括以下步骤：通过将复合带(20)螺旋卷绕到延伸的芯(10)以形成护套(16)，通过包裹或挤出施加具有含氟聚合物的外层(28)和烧结至少所述外层；其中所述复合带(20)包括具有分散有云母粒子的聚合物基质的第一层(24)和包含含有芳族环和/或杂环且具有至少350℃的熔点和150℃的玻璃化转变温度的聚合物的第二层(26)。
16.权利要求13的方法，其中所述烧结在350℃-420℃的温度下发生。
17.权利要求15或16的方法，其中所述外层(16)通过在高温下且在惰性气氛下施加电子束辐射来交联。
18.权利要求15-17中任一项的方法，其中使所述护套(16)在170-300℃下经受至多24小时的退火处理。
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Cited By (2)
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| CN104851528A (zh) * | 2015-04-30 | 2015-08-19 | 芜湖顺成电子有限公司 | 一种电线辐射交联工艺 |
Also Published As
| Publication number | Publication date |
|---|---|
| GB201008268D0 (en) | 2010-06-30 |
| GB2480452B (en) | 2014-10-08 |
| EP2571688B1 (en) | 2015-04-15 |
| JP2013533812A (ja) | 2013-08-29 |
| WO2011144933A1 (en) | 2011-11-24 |
| MX2012013326A (es) | 2012-12-05 |
| BR112012029050A2 (pt) | 2016-08-02 |
| US20130062097A1 (en) | 2013-03-14 |
| GB2480452A (en) | 2011-11-23 |
| EP2571688A1 (en) | 2013-03-27 |
| RU2012153914A (ru) | 2014-06-27 |
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