CN107383643A - 潜油泵电力用电缆耐油乙丙橡胶绝缘材料及其制备方法 - Google Patents

潜油泵电力用电缆耐油乙丙橡胶绝缘材料及其制备方法 Download PDF

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CN107383643A
CN107383643A CN201710772403.1A CN201710772403A CN107383643A CN 107383643 A CN107383643 A CN 107383643A CN 201710772403 A CN201710772403 A CN 201710772403A CN 107383643 A CN107383643 A CN 107383643A
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ethylene propylene
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蒋川扬
张会云
田维生
王伊雷
胡典栋
胡清平
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New Far East Cable Co Ltd
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Abstract

本发明公开了潜油泵电力用电缆耐油乙丙橡胶绝缘材料及其制备方法,由以下重量份数比的原料经混炼得到,三元乙丙橡胶80~100份、低密度聚乙烯8~18份、活化剂4~14份、增硬剂5~12份、软化剂22~37份、滑石粉6~50份、煅烧陶土60~90份、硫化体系4~6份、防老体系1.6~3.5份、偶联剂0.5~2.5份、加工助剂4~8份。本发明克服了现有技术中绝缘料交联密度不够、耐高热水绝缘电阻下降快,尤其耐复杂油井中石油基矿物液体的腐蚀不足,体积膨胀过大的缺陷,提供一种耐温耐油优异、挤出加工性能好、与导体粘接牢靠的潜油泵电缆绝缘材料。

Description

潜油泵电力用电缆耐油乙丙橡胶绝缘材料及其制备方法
技术领域
本发明涉及电缆橡胶材料技术领域,尤其涉及一种潜油泵电力用电缆耐油乙丙橡胶绝缘材料及其制备方法。
背景技术
目前,电力电缆是一种用于传输和分配电能的电缆,潜油泵用的电力电缆对于电缆的耐油性和耐热老化性的要求很高。绝缘层性能的好坏对电缆的整体性能产生很大的影响,直接关系到电缆是否正常运行。绝缘层可以采用交联聚乙烯、聚丙烯等聚烯烃材料,但耐高温一般采用乙丙橡皮材料。
潜油泵用的电力电缆,由于油井的高温环境和电在输送的过程中,电缆自身的电阻产生的热量很大,对于电缆的耐热性要求很高;由于潜油泵工作的环境复杂,要求电缆橡胶应具有高强度和耐油的性能来避免电缆因强度不够和原油腐蚀而造成电缆易损坏情况的出现,普通电缆所采用的电缆乙丙橡胶材料无法满足潜油泵环境中对于电缆橡胶材料性能的要求。
发明内容
本发明提出一种潜油泵电力用电缆耐油乙丙橡胶绝缘材料及其制备方法,其制备出的电缆橡胶材料具有高强度和高耐油性。
本发明提出了一种潜油泵电力用电缆耐油乙丙橡胶绝缘材料,其原料按重量份包括:
上述的潜油泵电力用电缆耐油乙丙橡胶绝缘材料,所述偶联剂为A-172、KH-570和KH~550硅烷偶联剂中的一种或多种组合。
上述的潜油泵电力用电缆耐油乙丙橡胶绝缘材料,所述活化剂为氧化锌、氧化镁和Pb3O4,氧化锌含量为1~4份、氧化镁含量为1~5份、Pb3O4含量为2~5份。
上述的潜油泵电力用电缆耐油乙丙橡胶绝缘材料,所述增硬剂为甲基丙烯酸锌,含量为5~12份。
上述的潜油泵电力用电缆耐油乙丙橡胶绝缘材料,所述软化剂为聚异丁烯和低1,2结构的聚丁二烯,聚异丁烯12~22份,低1,2结构的聚丁二烯10~15份。
上述的潜油泵电力用电缆耐油乙丙橡胶绝缘材料,所述硫化体系为硫化剂DCP和和硫化助剂VP-4,DCP 2~6份,硫化助剂VP-40.5~1份。
上述的潜油泵电力用电缆耐油乙丙橡胶绝缘材料,所述防老体系为防老剂MBZ和MC,防老剂MBZ 0.6~1.5份,MC 1~2份。
上述的潜油泵电力用电缆耐油乙丙橡胶绝缘材料,所述加工助剂为硬脂酸和微晶石蜡,硬脂酸1~3份,微晶石蜡3~5份。
本发明还提出了一种潜油泵电力用电缆耐油乙丙橡胶绝缘材料的制备方法,包括:
步骤一:配料:按照前述配方配料;
步骤二:混炼:将三元乙丙橡胶和低密度聚乙烯进行塑炼,得到塑炼胶,其中塑炼的时间为2~3min,塑炼的温度为90~100℃;
步骤三:向步骤二中得到的塑炼胶中添加氧化锌、氧化镁、硬脂酸、Pb3O4、聚异丁烯、甲基丙烯酸锌、低1,2结构的聚丁二烯进行一次混炼,得到一次混炼胶,其中一次混炼的时间为3~4min,一次混炼的温度为95~110℃;向一次混炼胶中添加滑石粉和煅烧陶土、低1,2结构的聚丁二烯进行二次混炼,得到二次混炼胶,其中,二次混炼的时间为2~3min,二次混炼的温度为120~140℃;
步骤四:向步骤三中得到的二次混炼胶中添加硫化剂DCP、硫化助剂VP-4、防老剂MBZ、防老剂MC、偶联剂、微晶石蜡进行三次混炼,得到三次混炼胶,其中,三次混炼的时间为1~3min,三次混炼的温度为98~102℃;
步骤五:出片:将步骤四中获得的三次混炼胶在开炼机上再翻炼二次后再在压延机上碾页,最终出片厚度0.6~0.7mm,过粉冷却18h以上,得到所述潜油泵电力用电缆耐油乙丙橡胶绝缘材料。
本发明的原理是:首先将三元乙丙橡胶和低密度聚乙烯进行塑炼,得到塑炼胶;然后向塑炼胶中添加氧化锌、氧化镁、硬脂酸、Pb3O4、聚异丁烯、甲基丙烯酸锌、低1,2结构的聚丁二烯进行一次混炼,得到一次混炼胶;接着向一次混炼胶中添加滑石粉和煅烧陶土进行二次混炼,得到二次混炼胶;最后向二次混炼胶中添加硫化剂DCP、硫化助剂VP-4、防老剂MBZ、防老剂MC、偶联剂、微晶石蜡进行三次混炼,得到三次混炼胶,将三次混炼胶冷却出料。本发明通过先塑炼,然后进行多步骤混炼,有效的提高了电缆橡胶材料中各组分的性能在混炼的过程中得到得到最大化的利用,进而整体提高了电缆橡胶材料的强度和耐油性;添加的低密度聚乙烯防止了因三元乙丙橡胶含量增加引起的耐油性的降低。低密度聚乙烯易与乙丙共混,所以选择熔融指数高的,粘度低,更好分散。同时添加滑石粉和煅烧陶土,起到了增大体积、降低成本、改善加工工艺的作用;添加的甲基丙烯酸锌在橡胶老化的过程中会进一步交联,保护屏蔽橡胶分子链,减少热氧的攻击,提高了电缆橡胶材料的强度、与导体的粘接性和耐油性;添加的聚异丁烯和低1,2结构的聚丁二烯以替代石蜡软化操作油,同时起助交联作用,提高了低分子组份的热迁移和耐热水性;通过添加硫化剂DCP和硫化助剂VP-4,提高了交联密度,改善了电缆橡胶材料的耐温性能。VP-4用量较低0.5-1.0份时,对DCP硫化的EPDM胶料的正硫化时间缩短,最大弹性转矩和交联密度增大,压缩永久变形值明显下降,具有明显的促进交联作用。VP-4有效地提高了硫化胶耐热空气老化性能,尤其是高温(150℃)时的耐热空气老化性能得到明显改善。交联速度和机械强度比单用过氧化物还有所提高,在三元乙丙和其它胶中用它代替硫黄,可消除加工硫化时的奇臭味,硫化速度快,能制得无气味、耐热,定伸应力高的硫化剂。防老剂MBZ是锌盐型防老剂,能有效地防护铜害和克服过硫引起的不良作用,与胺类、酚类抗氧剂产生协同效应,对过氧化物硫化的EPDM橡胶,具有优良的耐热性。反应性防老剂MC在硫化过程中形成的橡胶接枝产物和均聚产物,会消耗少量的DCP,分子中羰基的共轭作用,降低了胺基的活性,从而在过氧化物交联体系中减轻了对交联的干扰程度。防老剂MC参与硫化反应,形成EPDM/MC接枝产物,避免了被ASTM油抽出,从而使硫化胶老化后的力学性能得到保证。现有的防老剂4020、防老剂RD易于被极性相近的ASTM油抽出,导致老化后性能劣化。所以,MBZ+MC并用,具有优异的抗热老化能力,又有防油抽出,提高了耐油性能。
采用了上述技术方案,本发明的优点为:通过选择合适的组分,调节组分的含量,优化制备工艺,得到了高强度、高耐油性的潜油泵电力用电缆橡胶材料,应用到潜油泵用电力电缆中,延长了电缆的使用寿命和使用的安全性。
具体实施方式
下面结合具体实施例对本发明作出详细说明。
(实施例1)
本实施例的潜油泵电力用电缆耐油乙丙橡胶绝缘材料,其原料按重量份包括:
三元乙丙橡胶100份、低密度聚乙烯8份、氧化锌3份、氧化镁5份、硬脂酸1份、聚异丁烯15份、甲基丙烯酸锌10份、低1,2结构的聚丁二烯15份、滑石粉10份、煅烧陶土90份、硫化剂DCP 2份、硫化助剂VP-4 1份、防老剂MBZ 1份、防老剂MC 2份、偶联剂A-172 1.5份、Pb3O4 3份、微晶石蜡4份。
(实施例2)
本实施例的原料按重量份包括:三元乙丙橡胶100份、低密度聚乙烯12份、氧化锌5份、氧化镁5份、硬脂酸1份、聚异丁烯12份、甲基丙烯酸锌12份、低1,2结构的聚丁二烯8份、滑石粉20份、煅烧陶土80份、硫化剂DCP 3份、硫化助剂VP-4 0.5份、防老剂MBZ 2份、防老剂MC 1份、偶联剂A-172 1份、Pb3O4 2份、微晶石蜡3份。
(实施例3)
本实施例的原料按重量份包括:
潜油泵电力用电缆橡胶材料,其原料按重量份包括:三元乙丙橡胶100份、低密度聚乙烯15份、氧化锌7份、氧化镁3份、硬脂酸1份、聚异丁烯18份、甲基丙烯酸锌15份、低1,2结构的聚丁二烯6份、滑石粉30份、煅烧陶土70份、硫化剂DCP 4份、硫化助剂VP-4 1份、防老剂MBZ 1份、防老剂MC 2份、偶联剂A-172 2份、Pb3O4 4份、微晶石蜡5份。
(实施例4)
本实施例的原料按重量份包括:
潜油泵电力用电缆橡胶材料,其原料按重量份包括:三元乙丙橡胶100份、低密度聚乙烯10份、氧化锌6份、氧化镁5份、硬脂酸1份、聚异丁烯8份、甲基丙烯酸锌8份、低1,2结构的聚丁二烯15份、滑石粉40份、煅烧陶土60份、硫化剂DCP 5份、硫化助剂VP-4 0.5份、防老剂MBZ 1份、防老剂MC 2份、偶联剂A-172 1份、Pb3O4 5份、微晶石蜡5份。
制备方法包括:
(1)配料:按配方准确计量、称重各种材料;
(2)将三元乙丙橡胶和低密度聚乙烯进行塑炼,得到塑炼胶,其中塑炼的时间为2~3min,塑炼的温度为100℃;
(3)向(2)中得到的塑炼胶中添加氧化锌、氧化镁、硬脂酸、Pb3O4、聚异丁烯、甲基丙烯酸锌、低1,2结构的聚丁二烯进行一次混炼,得到一次混炼胶,其中一次混炼的时间为3~4min,一次混炼的温度为110℃;向一次混炼胶中添加滑石粉和煅烧陶土进行二次混炼,得到二次混炼胶,其中,二次混炼的时间为3min,二次混炼的温度为120℃,得到二次混炼胶;
(4)向(3)中得到的二次混炼胶中添加硫化剂DCP、硫化助剂VP-4、防老剂MBZ、防老剂MC、偶联剂、微晶石蜡进行三次混炼,得到三次混炼胶,其中,三次混炼的时间为1min,三次混炼的温度为90℃;
(5)将(4)中获得的三次混炼胶在开炼机上再翻炼二次后再在压延机上碾页,最终出片厚度0.6~0.7mm,过粉冷却18h以上,得到所述潜油泵电力用电缆耐油乙丙橡胶绝缘材料。
其中,所述偶联剂为A-172、KH-570硅烷偶联剂和KH-550硅烷偶联剂按任一比组合。
将上述各种材料混炼后的胶料的性能见下表:
以上所述的具体实施例,对本发明的目的、技术方案和有益效果进行了进一步详细说明,所应理解的是,以上所述仅为本发明的具体实施例而已,并不用于限制本发明,凡在本发明的精神和原则之内,所做的任何修改、等同替换、改进等,均应包含在本发明的保护范围之内。

Claims (9)

1.潜油泵电力用电缆耐油乙丙橡胶绝缘材料,其特征在于:所述组成及配比,以质量份计为:
所述三元乙丙橡胶为:ENB含量5.7,乙烯含量65,挥发度0.42,灰粉0.03,稳定剂N.S,125℃下测试的门尼粘度为23;低密度聚乙烯熔融指数为10~15。
2.根据权利要求1所述的潜油泵电力用电缆耐油乙丙橡胶绝缘材料,其特征在于:所述偶联剂为A-172、KH-570和KH-550硅烷偶联剂中的一种或多种组合。
3.根据权利要求1所述的潜油泵电力用电缆耐油乙丙橡胶绝缘材料,其特征在于:所述活化剂为氧化锌、氧化镁和Pb3O4的混合物;它们的含量分别为:氧化锌含量为1~4份、氧化镁含量为1~5份、Pb3O4含量为2~5份。
4.根据权利要求1所述的潜油泵电力用电缆耐油乙丙橡胶绝缘材料,其特征在于:所述增硬剂为甲基丙烯酸锌,含量为5~12份。
5.根据权利要求1所述的一潜油泵电力用电缆耐油乙丙橡胶绝缘材料,其特征在于:软化剂为聚异丁烯和低1,2结构的聚丁二烯,它们的含量分别为:聚异丁烯12~22份,低1,2结构的聚丁二烯10~15份。
6.根据权利要求1所述的潜油泵电力用电缆耐油乙丙橡胶绝缘材料,其特征在于:所述硫化体系为硫化剂DCP和和硫化助剂VP-4,它们的含量分别为:DCP1.2~2.6份,硫化助剂VP-40.5~1份。
7.根据权利要求1所述的潜油泵电力用电缆耐油乙丙橡胶绝缘材料,其特征在于:所述防老体系为防老剂MBZ和MC,它们的含量分别为:防老剂MBZ 0.6~1.5份,MC1~2份。
8.根据权利要求1所述的潜油泵电力用电缆耐油乙丙橡胶绝缘材料,其特征在于:所述加工助剂为硬脂酸和微晶石蜡,它们的含量分别为:硬脂酸1~3份,微晶石蜡3~5份。
9.根据权利要求1所述的潜油泵电力用电缆耐油乙丙橡胶绝缘材料的制备方法,其特征在于:包括以下步骤:
步骤一:配料:组成及配比,以质量份计为:
三元乙丙橡胶是ENB含量5.7,乙烯含量65,挥发度0.42,灰粉0.03,稳定剂N.S,125℃下测试的门尼粘度为23,低密度聚乙烯是熔融指数为10~15;偶联剂为A-172、KH-570和KH-550硅烷偶联剂中的一种或多种组合;活化剂为氧化锌、氧化镁和Pb3O4的混合物,它们的含量分别为:氧化锌含量为1~4份、氧化镁含量为1~5份、Pb3O4含量为2~5份;增硬剂为甲基丙烯酸锌,含量为5~12份;软化剂为聚异丁烯和低1,2结构的聚丁二烯,它们的含量分别为:聚异丁烯12~22份,低1,2结构的聚丁二烯10~5份;硫化体系为硫化剂DCP和和硫化助剂VP-4,它们的含量分别为:DCP1.2~2.6份,硫化助剂VP-40.5~1份;防老体系为防老剂MBZ和MC,它们的含量分别为:防老剂MBZ 0.6~1.5份,MC1~2份;加工助剂为硬脂酸和微晶石蜡,它们的含量分别为:硬脂酸1~3份,微晶石蜡3~5份。
步骤二:混炼:将三元乙丙橡胶和低密度聚乙烯进行塑炼,得到塑炼胶,其中塑炼的时间为2~3min,塑炼的温度为90~100℃;
步骤三:向步骤二中得到的塑炼胶中添加氧化锌、氧化镁、硬脂酸、Pb3O4、聚异丁烯、甲基丙烯酸锌、低1,2结构的聚丁二烯进行一次混炼,得到一次混炼胶,其中一次混炼的时间为3~4min,一次混炼的温度为95~110℃;向一次混炼胶中添加滑石粉和煅烧陶土、低1,2结构的聚丁二烯进行二次混炼,得到二次混炼胶,其中,二次混炼的时间为2~3min,二次混炼的温度为120~140℃;
步骤四:向步骤三中得到的二次混炼胶中添加硫化剂DCP、硫化助剂VP-4、防老剂MBZ、防老剂MC、偶联剂、微晶石蜡进行三次混炼,得到三次混炼胶,其中,三次混炼的时间为1~3min,三次混炼的温度为98~102℃;
步骤五:出片:将步骤四中获得的三次混炼胶在开炼机上再翻炼二次后再在压延机上碾页,最终出片厚度0.6~0.7mm,过粉冷却18h以上,得到所述潜油泵电力用电缆耐油乙丙橡胶绝缘材料。
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