CN104558860A - 用于制备具有增强的热稳定性的绝缘材料的聚合物树脂组合物 - Google Patents
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Abstract
本发明涉及聚合物树脂组合物,其包括作为基础树脂的EPDM(乙烯丙烯二烯单体),并且进一步包括基于100重量份的所述基础树脂的以下组分:-1~5重量份的基于胺的抗氧化剂,和-1~5重量份的HALS(受阻胺光稳定剂)。使用根据本发明的聚合物树脂组合物制造的绝缘材料具有良好的热稳定性以及在高温下延长的寿命。因此,其特别适合用在用于核电厂的电缆中。
Description
技术领域
本发明涉及用于制造具有增强的热稳定性的绝缘材料的聚合物树脂组合物。此外,本发明涉及使用该聚合物树脂组合物制造的绝缘材料,特别是用于在核电厂中使用的电缆的绝缘材料。
背景技术
在核电厂中使用的电缆通常由导体、绝缘体、屏蔽物和护套(jacket)构成。所述绝缘体在防止所述导体中流动的电流从所述导体流出和保持电压方面起作用。所述电缆的机械性能根据所述绝缘体中包含的添加剂而变化。
特别地,在核电厂中使用的电缆的特征在于,当核电厂运行时难以对它们进行更换,并且它们连续暴露于具有非常高温度的苛刻环境。因此,在所述电缆中的绝缘体或鞘(sheath)的老化被加速是通常的。当发生由于劣化引起的电气火灾时,这样的老化的电缆丧失它们自身的功能并且引起误操作。在这种情况下,核电厂的安全关闭功能未得以正常地执行,并且因此可能发生严重的安全事故。
因此,为了改善在核电厂中使用的电缆的耐热性和/或耐辐射性,在相关领域做出了许多努力。
举一个实例来说,韩国专利公布KR 10-2011-0070162 A1公开了通过将具有1.40~1.60eV活化能的另外的辅助材料置于电缆的芯和鞘之间而改善电缆的高温耐久性,并且该另外的辅助材料优选地用酚类抗氧化剂处理。然而,在所述公布的专利申请中,为了获得具有1.40~1.60eV活化能的另外的辅助材料,使用了用酚类抗氧化剂处理的对生态环境友好的材料HF-PO(不含卤素的聚烯烃)。
举另外一个实例来说,韩国专利KR 10-1216050 B1公开了通过以100∶40∶1∶0.5∶10的重量比包括EPDM、炭黑、交联剂、抗氧化剂和粘土增强材料而改善电缆的机械性能例如伸长率和拉伸强度、和耐辐射性。然而,在所述专利中,应当包括EPDM、炭黑、交联剂、抗氧化剂和粘土增强材料作为必要成分。
令人惊讶地,本发明人发现,由聚合物树脂组合物制造的电缆绝缘体的热稳定性,并且因此该电缆的寿命,特别是当连续暴露于高温时该电缆的寿命,取决于所述聚合物树脂组合物中包含的抗氧化剂的类型和混合比率而变化。至今,尚未有关于以下事实的详细研究:电缆绝缘体的热稳定性可以通过包括在聚合物树脂组合物中的抗氧化剂和UV稳定剂的某种组合而得以显著改善。
发明内容
本领域中的用于在核电厂中典型地使用的电缆的绝缘材料被制造成匹配40年的设计寿命。本发明的目的是显著改善电缆的绝缘材料的热稳定性并且提供用于匹配60年设计寿命的电缆的绝缘材料。
本发明的所述目的可通过包括如下的聚合物树脂组合物实现:基于100重量份的用作基础树脂的EPDM,1~5重量份的基于胺的抗氧化剂和1~5重量份的HALS。
用作根据本发明的聚合物树脂组合物的基础树脂的EPDM是乙烯丙烯二烯单体的首字母缩写。本发明人发现,由该聚合物树脂组合物制造的聚合物树脂材料的热稳定性在EPDM的组成改变时变化。为了更多地提高所述聚合物树脂材料的热稳定性,如下是优选的:所述EPDM中包含的ENB(乙叉降冰片烯)的含量为2~5重量%,特别是4~5重量%。此外,如下是优选的:所述EPDM中包含的乙烯的含量为50重量%或更多,特别是60重量%或更多,更特别是70重量%或更多。
与传统上使用酚类、亚磷酸酯或硫代酯类抗氧化剂来向基于EPDM的绝缘材料提供耐热性的事实不同,根据本发明的聚合物树脂组合物使用HALS和基于胺的抗氧化剂的组合以改善基于EPDM的绝缘材料的热稳定性。
所述基于胺的抗氧化剂包括,但不限于,TMQ(2,2,4-三甲基-1,2-二氢喹啉)等。
与所述基于胺的抗氧化剂组合使用的HALS是受阻胺光稳定剂的首字母缩写。其是2,2,6,6-四甲基哌啶的衍生物,并且在本领域中已知作为对于大部分聚合物的光诱导的分解而言非常有效的稳定剂。此外,HALS的特征在于,其在稳定化过程中得以再生,并且因此其可以长时间呈现良好的热稳定性和光稳定性。这样的HALS包括N-H型、N-R型、N-OR型等,并且其是可以多种商品名商购得到的。在本发明中,优选使用N-H型或N-R型的HALS,例如使用具有NH基团(一个或多个)或NCH3基团(一个或多个)的HALS。
根据一个优选的实施方案,所述聚合物树脂组合物进一步包括:基于100重量份的所述基础树脂,30~50重量份的基于卤素的阻燃剂,5~10重量份的基于锑的阻燃助剂,和5~15重量份的至少一种选自基于铅的化合物、基于金属皂的化合物和基于钙的化合物的稳定剂。
所述基于卤素的阻燃剂包括,但不限于,基于溴的阻燃剂例如TBBA(四溴双酚A)、基于氯的阻燃剂例如TCPP(磷酸三(1-氯-2-丙基)酯)等。
所述基于锑的阻燃助剂包括,但不限于,三氧化二锑等。
所述稳定剂选自基于铅的、基于金属皂的和基于钙的化合物。所述基于铅的稳定剂的实例包括PbO、TLS(三碱式硫酸铅)、DLS(二碱式硬脂酸铅)、DLP(二碱式亚磷酸铅)等;所述基于金属皂的稳定剂的实例包括Ba-St(硬脂酸盐)、Ca-St、Zn-St等;和所述基于钙的稳定剂的实例包括Ca-Zn-Mg、Ca-Zn-Al等,但对它们没有限制。
在根据本发明的一个具体实施方式中,所述聚合物树脂组合物为能交联的组合物。
所述能交联的组合物可通过本领域中公知的技术交联。
在此方面,所述聚合物树脂组合物可包括以足以使所述聚合物树脂组合物交联的量的至少一种交联剂。
例如,交联剂的量可为0.1~10重量份,基于100重量份的所述基础树脂。
所述交联剂可为有机过氧化物,例如过氧化二枯基(DCP)。
本发明的另一方面涉及包括至少一个被绝缘的导体的电缆,所述被绝缘的导体包括被至少一个绝缘层包围的至少一个伸长的电元件,所述绝缘层由根据本发明的聚合物树脂组合物制成。
所述电缆可进一步包括将所述被绝缘的导体(一个或多个)全部包围在一起的外鞘。
所述外鞘为用于机械保护所述电缆的所述被绝缘的导体(一个或多个)的保护鞘。
所述外鞘也可具有阻燃性。
更特别地,所述外鞘可由阻燃聚合物和/或具有阻燃填料的聚合物制成。
例如,所述外鞘可为由氯磺化聚乙烯制成的鞘,其提供良好的机械保护以及良好的阻燃性。
所述伸长的电元件可为单芯导体例如一根电线、或者多芯导体例如多根线(导线)。
所述伸长的电元件可由金属材料(例如,选自铝、铝合金、铜、铜合金、以及其任意组合的金属材料)制成。
在一个优选实施方式中,所述电缆可包括至少两个根据本发明的被绝缘的导体。
根据本发明的绝缘层可为物理地与所述伸长的电元件直接接触的层、或者为中间层、或者所述电缆的最外层。
在一个具体实施方式中,沿着所述电缆在所述伸长的电元件和所述绝缘层之间安置隔离体层。更特别地,所述隔离体层物理地与所述伸长的电元件直接接触。
所述隔离体层有利地容许容易地将所述绝缘层从所述伸长的电元件分离。
更优选地,所述隔离体为螺旋地包围所述伸长的电元件的带。例如,所述隔离体层可为聚酯带。
本发明的绝缘层更特别地为电绝缘层。
本发明的绝缘层可有利地为交联层。
在一个具体实施方式中,本发明涉及使用上述聚合物树脂组合物制备的聚合物树脂材料,特别是电缆或电线(更特别地在核电厂中使用的电缆或电线)的覆盖材料或绝缘体。
有益效果
使用其中规定了抗氧化剂的混合比例和类型的根据本发明的聚合物树脂组合物制造的绝缘材料在室温下具有良好的拉伸强度和伸长率。此外,其即使在超过100℃的高温下也具有高的拉伸强度保持率(tensile retention)和伸长保持率,并且因此显示出显著良好的耐热性。另外,对于电缆而言在根本上所需要的物理和化学性质例如阻燃性也是优异的。因此覆盖有根据本发明的绝缘材料的电缆或电线即使在高温的苛刻环境例如核电厂中也具有显著提高的寿命,并且因此是经济上划算的。
具体实施方式
实施例
在以下实施例中以及从附图进一步详细地描述本发明,所述实施例和附图绝不意图限制所要求保护的本发明的范围。此外,据本领域普通技术人员看来,可对所公开的实施方案进行各种修改,并且这样的修改意图在本发明的范围内。
1.样品的制备
使用具有在以下表1中列出的组分和量(以基于100份基础树脂的重量份呈现)的组合物,用工厂挤出机和当使用有机过氧化物时的通常的交联条件制备电缆的经交联的绝缘体。实施例1-4的聚合物树脂组合物是根据本发明的,并且对比例1-3的聚合物树脂组合物是本发明的范围之外的。由如上所述制备的电缆的每一个采集样品。
[表1]
(1):其中ENB的含量为4~5重量%和乙烯的含量为60~70重量%的EPDM。所述EPDM是由DuPont Dow Elastomers L.L.C商品化的,CAS号为25038-36-2。
(2):其中ENB的含量为3~4重量%和乙烯的含量为60~70重量%的EPDM。所述EPDM是由Lanxess商品化的,CAS号为61789-00-2。
(3):其中ENB的含量为2~3重量%和乙烯的含量为50重量%的EPDM。所述EPDM是由Mitsui Chemicals Inc商品化的,CAS号为25038-36-2。
(4):具有874的分子量的TMQ是由Addivant商品化的,CAS号为26780-96-1。
(5):具有173的分子量的TMQ是由Lanxess商品化的,CAS号为26780-96-1。
(6):N-H聚合物型HALS是由BASF商品化的,CAS号为71878-19-8。
在上表1中,使用以商品名PG-600可商购获得的滑石作为填料,使用硬脂酸作为加工助剂,和使用DCP作为交联剂。另外,使用TMQ作为基于胺的抗氧化剂。具有不同分子量的TMQ仅在它们的聚合度上有差别,但它们的耐热性能是无差别的。
2.一般测试评价
测试所采集的样品是否满足以下标准。
(1)室温性能标准
当根据IEC 60811-1-1使用250mm/分钟的拉伸速度测量时,拉伸强度应当为8.2MPa或更高,和伸长率应当为150%或更高。
(2)加热性能标准
在使样品处于121℃下168小时之后,测量样品的拉伸强度和伸长率的变化率。变化率的比较基于室温下的拉伸强度和伸长率,并且保持率各自应当为75%或更高。
(3)热延伸(hot set)性能标准
当在将20.4g/mm2重量的摆锤悬挂在各样品上的情况下使样品处于150℃的烘箱中10分钟时,样品的伸长的长度(即,在负载状态下的伸长率)应当为50%或更少。
然后,在从样品移除摆锤、使它们处于150℃的烘箱中5分钟、然后将它们在室温下冷却之后,样品的缩短的长度(即,冷却后的最大伸长率)应当为5%或更小。
(4)阻燃性标准
根据IEC 60332-2A类阻燃性测试标准对样品进行测试。当根据ASTMD2863测量材料的阻燃性时,氧指数应当为30%或更高。
[表2]
一般测试评价的结果
以上表2显示了对于使用实施例1-4和对比例1-3的组合物制造的样品获得的测试值。
根据实施例1-4的样品满足对于在室温下的拉伸强度和伸长率、以及在121℃下加热后的拉伸强度保持率和伸长保持率的所有评价标准。此外,所述样品还满足热延伸性能标准和阻燃性标准。
同时,根据对比例2和3的样品当在室温下测量时呈现出低于8.2MPa的拉伸强度,且因此不满足评价标准。另外,根据对比例1-3的所有样品呈现出低于75%的拉伸强度保持率和伸长保持率值,且因此不满足评价标准。
3.长期老化测试评价
该测试是根据IEC 60216预期绝缘材料的与耐热性相关的寿命。将样品在选自150-200℃范围的三个具体温度下加速老化至终点。所述终点设置在50%伸长率。使用由该加速老化测试获得的数据,即终点(50%伸长率时的时间)和温度,通过应用Arrehenius方程而预期样品的活化能和寿命。
以下式I是Arrehenius模型,并且是确定材料的活化能和寿命的基础。另外,以下式2表示当预先确定了活化能时加速老化温度和加速老化时间之间的关系,并且允许其预期在连续工作温度下材料的寿命。
[式1]
[式2]
其中,
t1=材料的寿命(小时);
T1=连续工作温度(绝对温度,K);
t2=加速老化时间(小时);
T2=加速老化温度(绝对温度,K);
E=活化能(eV);
R=玻尔兹曼常数,8.617×10-5(eV/K)。
[表3]
长期老化测试评价的结果
根据对于在核电厂中通常使用的常规绝缘材料(即,由使用TMQ和巯基甲基苯并咪唑的组合作为抗氧化剂的组合物得到的绝缘材料)进行的加速老化测试的结果,当连续工作温度为90℃时,提供约40年的寿命。
同时,根据对于根据本发明的绝缘材料进行的加速老化测试的结果,当连续工作温度为90℃时,提供了约60年的寿命。
4.附图说明
图1表示根据本发明的电缆的一个实例的横截面的具体实施方式。
如图1上所示的电缆10包括7根分别包括被绝缘和交联层2所包围的多根镀锡铜线的一根多芯导体1的被绝缘的电导体,所述绝缘层2是由根据本发明的聚合物树脂组合物获得的。
可任选地在多芯导体1和绝缘层2之间安置隔离体层(图1上未示出),所述隔离体为沿着该电缆螺旋地包围所述多芯导体的聚酯带。
这7根被绝缘的电导体被由氯磺化聚乙烯制成的保护鞘3所包围。
Claims (11)
1.包括作为基础树脂的EPDM(乙烯丙烯二烯单体)的聚合物树脂组合物,其中该组合物包括基于100重量的所述基础树脂的以下组分:
-1~5重量份的基于胺的抗氧化剂,和
-1~5重量份的HALS(受阻胺光稳定剂)。
2.根据权利要求1的聚合物树脂组合物,其中所述EPDM具有2~5重量%的ENB(乙叉降冰片烯)和50重量%或更多的乙烯。
3.根据权利要求2的聚合物树脂组合物,其中所述EPDM具有4~5重量%的ENB(乙叉降冰片烯)和60重量%或更多的乙烯。
4.根据权利要求1的聚合物树脂组合物,其中所述基于胺的抗氧化剂为2,2,4-三甲基-1,2-二氢喹啉。
5.根据权利要求1的聚合物树脂组合物,其中所述HALS具有NH或NCH3基团。
6.根据权利要求1的聚合物树脂组合物,其中所述组合物进一步包括基于100重量份的所述基础树脂的以下组分:
-30~50重量份的基于卤素的阻燃剂,
-5~10重量份的基于锑的阻燃助剂,和
-5~15重量份的至少一种选自基于铅的化合物、基于金属皂的化合物和基于钙的化合物的稳定剂。
7.根据权利要求1的聚合物树脂组合物,其中所述聚合物树脂组合物包括至少一种交联剂。
8.电缆,其包括至少一个被绝缘的导体,所述被绝缘的导体包括被至少一个绝缘层包围的至少一个伸长的电元件,其中所述绝缘层由根据权利要求1-7任一项的聚合物树脂组合物制成。
9.根据权利要求8的电缆,其中所述绝缘层为交联层。
10.根据权利要求8或9的电缆,其中所述电缆进一步包括将所述被绝缘的导体全部包围在一起的外鞘。
11.根据权利要求8-10任一项的电缆,其中所述电缆包括至少两个被绝缘的导体。
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