CN115050506A - 包覆层由可回收聚合物材料制备的线缆 - Google Patents
包覆层由可回收聚合物材料制备的线缆 Download PDFInfo
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Abstract
一种线缆,其包含:包含由传输元件组成的芯和由包覆材料制备的包覆层,所述包覆材料包含(i)回收线性低密度聚乙烯(r‑LLDPE),量为70‑95wt%,例如80‑90wt%;和(ii)乙烯‑醋酸乙烯酯共聚物(EVA),量为5‑30wt%,例如10‑20wt%;重量百分比是相对于组合物中聚合物材料总重量表示的。包覆层显示出与初用聚合物组合物相当的机械性能,并且在老化前后都比包含回收LLDPE但不含EVA的回收聚合物基组合物更好。EVA可以添加到r‑LLDPE中,或者作为之前LLDPE使用的结果,r‑LLDPE中已包含EVA。线缆还可包含围绕r‑LLDPE基包覆层并与之直接接触的皮层。
Description
本发明涉及包覆层由可回收聚合物材料制备的线缆。更具体地说,本发明涉及一种包含至少一个包含至少一个传输元件的芯和至少一个包覆层的线缆,所述包覆层是由包含从废料中获得的至少一种聚乙烯的回收聚合物材料制备。
利用从废料中获得的聚合物材料制造新产品的可能性,对于环境可持续性和降低成本来说,是一个越来越重要的问题。在线缆领域,已经做出了一些努力,以使用回收的聚合物材料,特别是从废料中获得的乙烯聚合物,来生产线缆包覆层,特别是线缆护套(或包套)。
US 2008/0304797涉及一种线缆,其包含至少一个包含包覆材料制备的包覆层的芯,所述包覆材料包含从废料获得的第一聚乙烯和密度高于0.940g/cm3的第二聚乙烯。第一聚乙烯可选自低密度聚乙烯(LDPE)、线性低密度聚乙烯(LLDPE)、极低密度聚乙烯(VLDPE)或其混合物。第一聚乙烯可以相对于包覆材料总重量30-90wt%之间的量存在于包覆材料中。为了保护包覆材料免受UV降解,包覆材料可进一步包含炭黑,其量优选为包覆材料总重量的2-5wt%之间。可向包覆材料中添加其它常规添加剂,例如玻璃颗粒、玻璃纤维、煅烧粘土、滑石或其混合物。
在Hamim,F.A.R.等人在(2016),J.Phys.Sci.,27(2),23-39的文章中,公开了具有不同共混物组成和相容剂的回收高密度聚乙烯(RHDPE)/乙烯-醋酸乙烯酯(EVA)共混物。通过加入6份聚乙烯接枝马来酸酐(PE-g-MAH)和己内酰胺马来酸酐(CL-MAH),可提高RHDPE/EVA共混物的相容性。所有共混物的拉伸强度随EVA含量的增加而显著降低。这归因于EVA的存在,因EVA的非晶态特性影响了RHDPE的结晶结构。与不相容的RHDPE/EVA共混物相比,用PE-g-MAH增容的共混物显示出更高的拉伸强度。
Czarnecka-Komorowska D.等人在Advances in Scienceand TechnologyResearch Journal,Vol.12,No.3,2018年9月第134-142页的文章中示出了对回收聚乙烯制备的薄膜性能的调研结果。对源自包装材料的LDPE和LLDPE进行再加工,未使共混物有明显程度的降解,且回收的rLDPE或rLLDPE的使用性能与初用聚乙烯相似。观察到再生LDPE的拉伸性能(如强度和断裂伸长率)显著提高。当回收材料为LLDPE时,观察到相反的行为。
CN103965537涉及自交联复合聚乙烯线缆材料,其包含低密度聚乙烯(LDPE)的回收材料、线性低密度聚乙烯(LLDPE)的回收材料、高密度聚乙烯(HDPE)的回收材料、聚乙烯蜡、热稳定剂、耐寒剂、硅烷。
申请人注意到,回收聚合物材料提供的线缆包覆层的机械性能通常比从初用聚合物材料获得的要差。此外,此类包覆层可能具有较差的外观和/或粘性表面。这些问题可以通过将回收的聚合物材料与初用材料混合来解决,初用材料的量通常至少为10%w。当然,这就降低了单独使用回收聚合物的环境和经济优势。此外,一些掺混物回收/初用聚合物无法解决问题或产生新的问题。
申请人面临的技术问题是要提供可用于生产线缆包覆层、特别是线缆护套的可回收聚合物材料,其中回收材料是包覆层中主要存在或甚至是唯一的聚合物材料,其具有令人满意的机械性能,特别是拉伸和断裂伸长率,以及良好的表面外观。
申请人发现,上述技术问题和其它问题可以通过提供一种线缆来解决,该线缆的包覆层由包含70-95wt%回收线性低密度聚乙烯(r-LLDPE)、5-30wt%乙烯-醋酸乙烯酯共聚物(EVA)的组合物来制备,重量百分比是相对于组合物中聚合物材料总重量表示的。
因此,根据第一方面,本发明涉及一种线缆,其包含:包含传输元件的芯和由包覆材料制备的包覆层,所述包覆材料包含:
(i)回收线性低密度聚乙烯(r-LLDPE),量为70-95wt%,例如80-90wt%;和
(ii)乙烯-醋酸乙烯酯共聚物(EVA),量为5-30wt%,例如10-20wt%;
重量百分比是相对于组合物中聚合物材料总重量表示的。
就本说明书和所附权利要求而言,术语线缆的“芯”用于表示包含以下元件的半成品结构:传输元件例如电能传输元件、光信号传输元件或同时传输电能和光信号的元件,和至少一个电绝缘元件或分别地至少一个外护套元件(例如管、护套、微护套或槽芯),或在相关传输元件的径向外部位置布置至少两个元件,其中一个是电绝缘元件,一个是外护套元件。
就本说明书和所附权利要求而言,术语“电能传输元件”用于表示能够携带电能的任何元件,例如金属导体元件。作为一个说明性的例子,如果我们考虑用线缆来传输或分配中/高电压电能(中压是指约1-30kV之间的电压,而高压是指大于约30kV的电压),线缆的“芯”进一步包含至少一个布置在导体元件径向外部位置的内半导电包覆层,或者布置在电绝缘元件径向外部位置的外半导电包覆层。此外,通常在所述外半导体包覆层径向外部位置提供一个金属屏蔽。
就本说明书和所附权利要求而言,术语“光信号传输元件”用于表示包含至少一根光纤的任何传输元件。因此,该术语既可指单根光纤,也可指多根光纤,任选地集束在一起以形成光纤束,或彼此平行排列并用共同包覆层包覆以形成光纤带。作为一个说明性的例子,如果我们考虑光缆,线缆的“芯”可进一步包含阻水/吸收材料如凝胶,将传输元件嵌入到外护套层中。
就本说明书和所附权利要求而言,术语“混合型电-光传输元件”用于表示能够根据上述定义能传输电能和光信号二者的任何元件。
就本说明书和所附权利要求而言,术语“包覆层”指为保护目的沉积于线缆传输元件周围的任何包覆层,例如用于防止传输元件在制造、安装和使用过程中因机械应力而受损;该包覆层也可称为“护套”或“包套”。
本发明还涉及提供具有多根如上定义的芯线的线缆,在本领域中众所周知,根据其中包含的芯线数(在所述情况下,分别为两根、三根或更多根芯),术语称为“双极线缆”、“三极线缆”和“多极线缆”。
根据上述定义,本发明涉及提供具有一或多种任何类型芯线的线缆。换句话说,本发明涉及用于传输或分配电能的电导型、或包含至少一根光纤的光导型、或混合型电能/通讯型的单极或多极线缆。
就本说明书和所附权利要求而言,除非另有说明,否则所有表示量、数量、百分比等的数字应理解为在所有情况下都由术语“约”修饰。此外,所有范围包含所公开的最高点和最低点的任何组合,且包含其中的任何中间范围,本文可能会或可能不会具体列举。
本发明的至少一个方面可以根据本发明的一或多个、任选组合一起的实施方案来实现。
就本说明书和所附权利要求而言,词语“一个”应被理解为包含一个或至少一个,并且单数也包含复数,除非明显其另有含义。这样做仅仅是为了方便和给出本发明的一般含义。
就本说明书和所附权利要求而言,组合物中各组分的量表示为相对于组合物中聚合物材料总重量的重量百分比wt%,除非另有规定。
关于r-LLDPE(回收线性低密度聚乙烯),其可以是通过回收包含或基本上由LLDPE组成的物品获得的LLDPE,例如用于农业的地膜或包装膜。在一个实施方案中,r-LLDPE的密度可为0.850-0.926g/cm3,按照标准方法ASTM D792-00测量。本领域众所周知,LLDPE是指一类具有短支链的乙烯共聚物,通过乙烯与少量α-烯烃C3-C12(例如1-丁烯、1-己烯或1-辛烯)共聚获得。LLDPE可以在齐格勒-纳塔催化剂、铬催化剂或茂金属催化剂存在下通过低压共聚工艺生产。共聚物中α-烯烃C3-C12的摩尔含量为1-15%。
在一个实施方案中,r-LLDPE的熔体流动指数(MFI;也称为熔体流动速率MFR或熔融指数)为0.8-10g/10min(按照ASTM D1238-04或ISO 1133-00,190℃,2.16kg)。
关于乙烯-醋酸乙烯酯共聚物(EVA),它通常是由乙烯与醋酸乙烯酯高压共聚来生产的。EVA中醋酸乙烯酯的量可为10-40wt%,例如15-30wt%。
EVA可以添加到r-LLDPE中,或者作为之前LLDPE使用的结果已包含在r-LLDPE中。在后一种情况下,EVA也被回收利用。r-LLDPE(回收EVA)中已包含的EVA量可通过FT-IR(傅里叶变换红外光谱)分析确定。
本发明包覆层的组合物可包含5-50wt%的初用或另外的回收聚乙烯均聚物或共聚物。初用聚乙烯可以是例如LLDPE或HDPE;另外的回收聚乙烯可以是HDPE。添加LLDPE可有助于提高本组合物的柔韧性,而添加初用或回收HDPE可有助于提高本组合物的硬度。
在一个实施方案中,本包覆层的组合物可进一步包含1至25wt%、例如1-8wt%量的防粘剂。
关于防粘剂,它可以是滑石、高岭土、碳酸钙、白垩、硬脂酸和硬脂酸盐如硬脂酸锌、铝、钙、镁、钠盐中的至少一种。添加防粘剂旨在避免组合物的粘连,无论是当组合物被还原成细碎形式例如待加工的颗粒或珠粒时,或者当它被施用于线缆芯上时。
组合物可包含其它添加剂,例如:抗氧化剂、阻燃剂、光或UV稳定剂、加工助剂、润滑剂、颜料、热稳定剂或其混合物。
在一个实施方案中,组合物可包含0.5-10wt%、例如1-5wt%量的炭黑。炭黑可用于防止聚合物材料的UV降解,或用作满足标准要求的颜料。
根据本发明的包覆层可以根据已知的挤出技术生产。在一个实施方案中,组合物以细碎形式被送入配有输送线缆芯的挤出头的挤出机。组合物在挤出机内熔融并混合,任选过滤,然后沉积在线缆芯周围。将如此包覆的线缆冷却并收集于卷轴上。
根据本发明的线缆可进一步包含位于基于r-LLDPE的包覆层周围并与之直接接触的皮层。皮层可由初用聚乙烯制备,旨在改善表面外观。此外,当包覆层仍有点粘时,可使用皮层。在皮层由初用HDPE制成时,可以为包覆层提供某些应用中所需的硬度。
皮层的厚度可为包覆层厚度的1-20%。
本发明线缆的包覆层可以是外护套(又称包套)。它可能是最外层的线缆层,除非存在皮层。
附图简要说明
参考附图,从以下给出的一些实施例的描述,更多特征和优点将更加显而易见,其中:
-图1示出了根据本发明一个实施方案的电力线缆截面图;
-图2示出了根据本发明另一个实施方案的电力线缆截面图。
图1示出了由四个线缆芯2组成的低压(LV)线缆1。每个线缆芯2包含由铜或铝等金属或其复合材料制备的电导体2a,其形式为成束或绞合线或单杆。每个电导体2a被绝缘层2b包围。绝缘层2b可以由聚乙烯等聚合物材料制备。
四个线缆芯2绞合在一起,并至少部分嵌入由聚合物材料制备的填料5中。填料被根据本发明聚合物组合物制备的护套或包套3所包围。
图2的线缆与图1的不同之处在于,根据本发明,护套3被皮层4所包围。
实施例1
测试以下聚合物材料:
M1(参考(reference)材料):密度为0.923g/cm3并添加2.5wt%炭黑(最终密度:0.936g/cm3;MFI=0.85g/10min)的初用LLDPE;
M2:从含有5.6wt%EVA的地膜回收的LLDPE,密度=0.969g/cm3;
M3(比较例):65-75wt%回收低密度聚乙烯(LDPE)+25-35wt%回收LLDPE+少于5wt%回收聚丙烯(PP),MFI=0.8-1.1g/min,密度=0.920-0.930g/cm3;
M4(比较例):含有少于40wt%回收LLDPE的回收LDPE,MFI=0.7-1.0g/min,密度=0.920-0.935g/cm3;
M5(比较例):回收高密度聚乙烯(HDPE),MFI=0.5g/min,密度=0.95g/cm3;
M6(比较例):回收高密度聚乙烯(HDPE),MFI=0.2g/min,密度=0.96g/cm3;
M7:70wt%M2+30wt%M1;
M8:M2添加炭黑(2.5wt%);
M9:M2添加白垩(5.0wt%)+炭黑(2.5wt%);
M10:M2添加滑石粉(2.5wt%)+炭黑(2.5wt%);
M11(比较例):M4添加炭黑(2.5wt%);
M12:M2添加滑石粉(2.5wt%)。
材料M1、M7、M8、M9、M10和M12是根据本发明。上述材料进行如下测试。
制膜.
将测试材料的颗粒以约150-250毫升的分批量放置在Schwabenthan实验室测试辊磨机的辊之间。滚距小于3毫米。将获得的膜部分切割并自我折叠,然后再送回辊磨机,以使其尽可能均匀。然后,将辊距增加到一定程度以从辊磨机中取出均匀的膜。在将膜放入聚合物压机之前将膜放置冷却以使聚合物均质化并产生宽度均匀的样片。
制备测试用试样
将聚合物膜切割以适配1mm厚的金属模板。模板内的薄膜放在两个聚酯覆盖之间,以防止聚合物和金属之间的粘附。最后,在放入压力机之前,将覆盖放置在两个金属平板之间。压机有两个隔室,一个较低,一个较高。将样品分别放入每个隔室中。在最初的10分钟内,将隔室加热至180℃,然后开始冷却。将压力设置为1bar持续5分钟,将压力设置为10bar持续10分钟,然后最后5分钟处于冷却状态。在压机内放置15分钟后,对样品进行加热、压制和冷却。移出板材、覆盖和金属模板,用扳手将样品固定成哑铃。
拉伸强度(TS)和断裂伸长率(EB)试验.
哑铃试样按照瑞典标准SS 424 14 18(2007)和SS-EN 60811-100(2014)进行拉伸试验,初始拉伸速度为25mm/min。对5个试样进行老化前后测试。
通过将每种材料的五个试样置于100℃的烘箱中240小时来进行老化。将试样从烘箱中取出,在室温下保持至少16小时,然后如上所述再次评估拉伸性能。
结果见表1。
表1
试样 | TS(MPa)老化前 | TS(MPa)老化后 | EB(%)老化前 | EB(%)老化后 |
M1* | 27.9 | 25.8 | 808.7 | 828.0 |
M2 | 28.9 | 26.5 | 828.9 | 813.0 |
M3* | 19.9 | 17.5 | 727.2 | 730.4 |
M4* | 24.0 | 24.3 | 693.0 | 747.0 |
M5* | 26.1 | 26.3 | 880.5 | 453.8 |
M6* | 32.3 | 33.5 | 966.7 | 1010.3 |
M7 | 27.8 | 25.8 | 835.4 | 836.9 |
M8 | 27.6 | - | 828.4 | - |
M9 | 25.2 | 24.6 | 788 | 833.9 |
M10 | 28.7 | 24.8 | 830 | 840.3 |
M11* | 26.3 | 22.5 | 780 | 780.1 |
*比较例
如表1所示,根据本发明的组合物(M2、M7、M8、M9和M10)的机械性能与初用聚合物组合物(M1)的机械性能相当,并且在老化前后均优于含有回收LLDPE(M3、M4)但不含EVA的回收聚合物基组合物。含有回收HDPE(M5,M6)的组合物由于聚乙烯的密度较高而表现出更好的性能。
低温试验
将每种材料的三个试样置于-20℃的冷室中至少16小时。然后将样品置于室温下,用扳手夹住并固定两端。两端之间的距离是l0。通过使用每五秒旋转一圈的转轴,施用约20mm/min的伸长速度。
按实施例1评估样品的断裂伸长率(EB),结果见表2。
表2
试样 | EB(%)低温处理后 |
M2 | >200 |
M4* | >200 |
M5* | 25 |
M6* | 70.8 |
虽然根据本发明的组合物(M2)在低温处理后保持适当的机械性能,但包含回收HDPE(M5,M6)的组合物有显著的下降,这使得其用于线缆护套的用途成问题。
根据ASTM D1693-13,使用100%Igepal对机械特性与M10相似的M12进行了环境应力开裂性(ESCR)测试。超过1000小时后,未观察到任何缺陷。
实施例2
生产了4000m N1XE-AS 4G95 0.6/1kV线缆,其护套由根据本发明的组合物或从实施例1选择的比较例组合物来制备。一些线缆提供有初用聚合物材料的皮层,其厚度为外护套厚度的10%。
对外护套样品进行拉伸和断裂伸长率试验。特别地,对从线缆上拆下的外护套样品进行了在100℃下老化240小时前后的试验。
结果见表3。
表3
ο密度为0.936g/cm3并添加2.5%炭黑的中密度聚乙烯(最终密度:0.948g/cm3;MFI=0.7g/10min);
οο高密度聚乙烯(密度:0.950g/cm3;MFI=0.3g/10min)
用对比例组合物(M4)制成的线缆外护套在挤出之后甚至在老化之前就具有不适合线缆的机械特性,但是用本发明组合物制造的线缆外护套在老化之后也具有合适的机械特性。由初用聚乙烯材料制成的皮层的存在并没有显着改变机械特性。
Claims (16)
1.线缆(1),其包含:包含传输元件(2a)的芯(2)和由包覆材料制备的包覆层(3),所述包覆材料包含:
(i)回收线性低密度聚乙烯,量为70-95wt%;和
(ii)乙烯-醋酸乙烯酯共聚物,量为5-30wt%;
重量百分比是相对于组合物中聚合物材料总重量表示的。
2.根据权利要求1的线缆,其中所述乙烯-醋酸乙烯酯共聚物是回收的。
3.根据权利要求1的线缆,其中所述包覆材料包含回收线性低密度聚乙烯,其量为组合物中存在的聚合物材料总重量的80-90wt%。
4.根据权利要求1的线缆,其中所述包覆材料包含乙烯-醋酸乙烯酯共聚物,其量为组合物中存在的聚合物材料总重量的10-20wt%。
5.根据权利要求1的线缆,其中所述包覆材料包含初用聚乙烯均聚物或共聚物,其量为组合物中存在的聚合物材料总重量的5-50wt%。
6.根据权利要求1的线缆,其中所述包覆材料包含另外的回收聚乙烯均聚物或共聚物,其量为组合物中存在的聚合物材料总重量的5-50wt%。
7.根据权利要求5的线缆,其中所述初用聚乙烯均聚物或共聚物选自线性低密度聚乙烯和高密度聚乙烯。
8.根据权利要求6的线缆,其中所述另外的回收聚乙烯均聚物或共聚物为回收的高密度聚乙烯。
9.根据权利要求1的线缆,其中所述包覆材料进一步包含防粘剂,其量为组合物中存在的聚合物材料总重量的1-25wt%。
10.根据权利要求9的线缆,其中所述防粘剂的量为组合物中存在的聚合物材料总重量的1-8wt%。
11.根据权利要求9的线缆,其中防粘剂是滑石、高岭土、碳酸钙、白垩、硬脂酸和硬脂酸盐中的至少一种。
12.根据权利要求1的线缆,其中所述包覆材料包含炭黑。
13.根据权利要求12的线缆,其中炭黑的量为组合物中存在的聚合物材料总重量的0.5-10wt%。
14.根据权利要求1的线缆,其进一步包含围绕包覆层(3)并与包覆层(3)直接接触的皮层(4)。
15.根据权利要求14的线缆,其中皮层(4)由初用聚乙烯制成。
16.根据权利要求14的线缆,其中皮层(4)的厚度为包覆层(3)厚度的1-20%。
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CN105086076A (zh) | 2015-08-20 | 2015-11-25 | 晶锋集团股份有限公司 | 一种添加废旧塑料的环保电缆护套料及其制备方法 |
CN105778234A (zh) | 2016-04-20 | 2016-07-20 | 朱加尖 | 一种环保节约型聚乙烯护套料及其制备方法 |
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