CN109021337A - 一种耐油耐热的高韧性电缆料 - Google Patents
一种耐油耐热的高韧性电缆料 Download PDFInfo
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- CN109021337A CN109021337A CN201810853379.9A CN201810853379A CN109021337A CN 109021337 A CN109021337 A CN 109021337A CN 201810853379 A CN201810853379 A CN 201810853379A CN 109021337 A CN109021337 A CN 109021337A
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- 239000003795 chemical substances by application Substances 0.000 claims abstract description 42
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Abstract
本发明涉及电力电缆技术领域,具体涉及一种耐油耐热的高韧性电缆料。电缆料的组分包括:丁腈橡胶、天然橡胶、高密度聚乙烯、氯磺化聚乙烯、马来酸酐接枝聚乙烯、催化交联剂、增塑剂、填料、硬脂酸镁、硫磺、偶联剂和防老剂。其中催化交联剂是一种用于促进聚烯烃材料和橡胶材料发生交联反应的促进剂,填料为钛白粉、轻质碳酸钙、氧化锌和MT炭黑按照5:4:2:1的质量比混合的混合填料;偶联剂为硅烷偶联剂;防老剂为防老剂RD、防老剂D或防老剂264。该型电缆料具有突出的耐油性和耐腐蚀性能,抗老化性能突出,机械强度高,柔韧性好;适用于机械船舶用特殊电缆的护套制备。
Description
技术领域
本发明涉及电力电缆技术领域,具体涉及一种耐油耐热的高韧性电缆料。
背景技术
电网是电力系统中联系发电和用电的设施和设备的统称。属于输送和分配电能的中间环节,它主要由联结成网的送电线路、变电所、配电所和配电线路组成。通常把由输电、变电、配电设备及相应的辅助系统组成的联系发电与用电的统一整体称为电力网,简称电网。电网的出现解决用电和发电市场的地理位置不一致的问题,让远程输电成为可能,远程输送电为了降低线路上的电力损耗,通常采用高压电进行输送;然后在用电端将电压降低至低压,通过电缆输送向电力用户,电网的安全运行离不开形形色色的电缆。
电缆根据用途包括电力电缆、控制电缆、补偿电缆、屏蔽电缆、信号电缆等不同种类,电缆料是电线电缆绝缘及护套用塑料的俗称,所用高分子材料主要有聚烯烃、氟塑料、氯化聚醚、橡胶和聚酰胺等,这类高分子材料具有质量轻、绝缘性能好、易加工、力学及抗疲劳性能优良等特点。
很多像是炼化工厂,海洋船舶和高温车间等场所也需要布设电缆,这些场所的空间一般具有高温,重油、强氧化、强腐蚀的特点,因此对于电缆护套材料的性能要求相对较高。但是常规的聚烯烃型电缆料的耐油、耐腐蚀性能普遍较差,因此在一些对电缆耐腐蚀抗氧化要求较高的场景下,使用聚烯烃电缆料作为护套材料的电缆往往难以达到性能要求。为了提高电缆料的耐油和耐腐蚀性能,还可以选择一种橡胶型电缆料,丁腈橡胶和氟橡胶等特种橡胶均具有很好的耐油性,但是这种橡胶材料的耐水性较差,容易发生溶胀,耐高温性能也相对不足,作为电缆料使用时加工工艺难度也更高,存在不可忽视的性能缺陷。因此如何开发出一种耐油、耐腐蚀,稳定好,且具有很好的电学性能和机械性能的电缆料,成为一个亟需解决的问题。
发明内容
针对现有技术中存在的问题,本发明提供了一种耐油耐热的高韧性电缆料,该型电缆料具有突出的耐油性和耐腐蚀性能,抗老化性能突出,机械强度高,柔韧性好;适用于机械船舶用特殊电缆的护套制备。
为了达到上述目的,本发明通过以下技术方案来实现的:
一种耐油耐热的高韧性电缆料,按照质量份数,电缆料的组分包括:丁腈橡胶40-60份,天然橡胶25-30份,高密度聚乙烯30-35份,氯磺化聚乙烯8-15份,马来酸酐接枝聚乙烯3-5份,催化交联剂2-4份,增塑剂4-6份,填料30-35份,硬脂酸镁2-3份,硫磺1-3份,偶联剂1-3份,防老剂1-2份。
优选地,按照质量份数,电缆料的组分包括:丁腈橡胶48-55份,天然橡胶27-29份,高密度聚乙烯31-34份,氯磺化聚乙烯10-13份,马来酸酐接枝聚乙烯3.4-4.3份,催化交联剂2.5-3.7份,增塑剂4.5-5.6份,填料32-34份,硬脂酸镁2.4-2.8份,硫磺1.7-2.3份,偶联剂2-2.4份,防老剂1.2-1.5份。
进一步优选地,按照质量份数,电缆料的组分包括:丁腈橡胶50份,天然橡胶28份,高密度聚乙烯32份,氯磺化聚乙烯12份,马来酸酐接枝聚乙烯4份,催化交联剂3.3份,增塑剂4.8份,填料33份,硬脂酸镁2.5份,硫磺2份,偶联剂2.1份,防老剂1.3份。
本发明中,催化交联剂的制备方法包括如下步骤:
(1)按照质量份数,准备以下原料:超稳定Y型沸石45.5份,轻质二氧化硅15份,α-氧化铝18.3份,氧化锆3.7份,三辛基胺10.2份,羟丙基淀粉醚2.3份,去离子水200份,将以上物质混合均匀后配制成料浆,料浆以80-95℃的温度搅拌反应30-40min,然后经自然沉降后,过滤并烘干得到干粉;
(2)将干粉先送入到还原气氛的高温炉中,以450-600℃的温度煅烧1-2h,然后再送入到氧化气氛的高温炉中煅烧2-3h,煅烧结束后出窑,并自然冷却至室温,将75份产物送入到1000份1.2-1.5mol/L的氢氧化钾溶液中,浸渍搅拌,并以40-50℃的水浴温度处理1-1.5h,然后将分散液减压蒸发浓缩后,雾化干燥得到载体微粉;
(3)将12份还原性镁化合物,7.5份叔丁氧基铝,2.5份一氯二乙基铝加入到反应釜中,在氮气气氛的保护下,向反应釜内加入50份正辛烷溶剂和2份烷基糖苷,搅拌至分散均匀,然后将载体微粉加入,以110-120℃的温度保温加热反应1.5-2.5h;反应结束后将产物冷却至室温,过滤得到固形物;
(4)将钛酸丁酯、异丙醇、二亚乙基三胺、过氧化苯甲酰和α-氨基吡啶按照2:5:1:2:2的质量比,加入到10倍体积的二甲苯溶剂中,搅拌分散得到改性剂,然后将50份上步骤得到的固形物加入到150份改性剂中,搅拌分散反应45-60min,然后将产物过滤后,以150-160℃的温度烘干处理,得到所需催化交联剂。
其中,步骤(2)中的高温炉内的还原气氛为氢气,氧化气氛为氧气。
步骤(3)中还原性镁化合物为二甲基镁、二丁基镁、丁基氯化镁和丁基乙氧基镁中的一种。
优选地,增塑剂为邻苯二甲酸二甲酯、邻苯二甲酸二丁酯、邻苯二甲酸二仲辛酯、邻苯二甲酸二环己酯、邻苯二甲酸二异壬酯和邻苯二甲酸二异癸酯中的一种。
优选地,填料为钛白粉、轻质碳酸钙、氧化锌和MT炭黑按照5:4:2:1的质量比混合的混合填料。
优选地,偶联剂为硅烷偶联剂;防老剂为防老剂RD、防老剂D或防老剂264。
本发明提供的电缆料的制备方法为:
按照质量份数,将密炼机预热至55-65℃,加入丁腈橡胶、天然橡胶和氯磺化聚乙烯,密炼处理10-13min,然后将高密度聚乙烯、马来酸酐接枝聚乙烯、催化交联剂和硫磺加入到密炼机中,以145-150℃的温度继续密炼6-8min,密炼结束后排料,混合料送入到烘箱中以170℃的温度高温硫化2-3h,然后自然冷却至室温,接着将混合料和填料、硬脂酸镁、增塑剂、偶联剂、防老剂一起投入到双螺杆挤出机中,以155-165℃的温度,300-350r/min的转速,经双螺杆挤出机混炼塑化并挤出造粒,得到所需电缆料。
本发明具有如下的有益效果:
该型电缆料是一种复合材料,主要由聚烯烃、橡胶和无机填料复合制备而成,其中橡胶材料包括丁腈橡胶和天然橡胶,聚烯烃材料为高密度聚乙烯和氯磺化聚乙烯,氯磺化聚乙烯可以和橡胶材料产生协同作用,显著提高复合材料的耐油耐腐蚀性能;材料中还采用马来酸酐接枝聚乙烯来作为相容剂,来提高两类高分子材料之间的结合效果。其中,为了使得这些高分子材料之间实现网格状交联,特意在密炼加工过程在使用催化交联剂和硫磺,经过催化交联剂的催化和促进作用,高分子材料可以在密炼机中发生预交联作用,显著提高材料间的相容性和结合作用,接下来经过硫磺和烘箱内的加热硫化处理,高分子材料中可以形成立体的网格状结构,大大提升复合材料的抗拉强度、断裂伸长率等机械性能;耐腐蚀、抗老化、耐高温等耐候性能,以及绝缘和电学耐击穿性能。
本发明中还通过硬脂酸镁作为润滑剂,和塑化剂、偶联剂、防老剂等功能助剂一起,提高材料的加工性能和材料稳定性。其中,使用的复合填料对于提高电缆料的强度和耐候性也非常重要,填料的组分包括钛白粉、轻质碳酸钙、氧化锌和MT炭黑,前两者作为填充加强剂使用,并与MT炭黑成分中的氢氧化铝成分构成阻燃剂,提高电缆料的阻燃性能;氧化锌和MT炭黑中的炭黑、纳米二氧化硅成分可以发挥活性剂的作用,大大提高电缆料的交联效果。
具体实施方式
下面结合实施例对本发明的具体实施方式作进一步描述,以下实施例仅用于更加清楚地说明本发明的技术方案,而不能以此来限制本发明的保护范围。
以下实施例中,催化交联剂的制备方法包括如下步骤:
(1)按照质量份数,准备以下原料:超稳定Y型沸石45.5份,轻质二氧化硅15份,α-氧化铝18.3份,氧化锆3.7份,三辛基胺10.2份,羟丙基淀粉醚2.3份,去离子水200份,将以上物质混合均匀后配制成料浆,料浆以90℃的温度搅拌反应35min,然后经自然沉降后,过滤并烘干得到干粉;
(2)将干粉先送入到还原气氛的高温炉中,以500℃的温度煅烧1.5h,然后再送入到氧化气氛的高温炉中煅烧3h,煅烧结束后出窑,并自然冷却至室温,将75份产物送入到1000份1.5mol/L的氢氧化钾溶液中,浸渍搅拌,并以45℃的水浴温度处理1h,然后将分散液减压蒸发浓缩后,雾化干燥得到载体微粉;
(3)将12份还原性镁化合物,7.5份叔丁氧基铝,2.5份一氯二乙基铝加入到反应釜中,在氮气气氛的保护下,向反应釜内加入50份正辛烷溶剂和2份烷基糖苷,搅拌至分散均匀,然后将载体微粉加入,以115℃的温度保温加热反应2h;反应结束后将产物冷却至室温,过滤得到固形物;
(4)将钛酸丁酯、异丙醇、二亚乙基三胺、过氧化苯甲酰和α-氨基吡啶按照2:5:1:2:2的质量比,加入到10倍体积的二甲苯溶剂中,搅拌分散得到改性剂,然后将50份上步骤得到的固形物加入到150份改性剂中,搅拌分散反应50min,然后将产物过滤后,以155℃的温度烘干处理,得到所需催化交联剂。
其中,步骤(2)中的高温炉内的还原气氛为氢气,氧化气氛为氧气。
步骤(3)中还原性镁化合物为丁基氯化镁。
实施例1
一种耐油耐热的高韧性电缆料,按照质量份数,电缆料的组分包括:丁腈橡胶40份,天然橡胶25份,高密度聚乙烯30份,氯磺化聚乙烯8份,马来酸酐接枝聚乙烯3份,催化交联剂2份,增塑剂4份,填料30份,硬脂酸镁2份,硫磺1份,偶联剂1份,防老剂1份。
其中,增塑剂为邻苯二甲酸二甲酯。
填料为钛白粉、轻质碳酸钙、氧化锌和MT炭黑按照5:4:2:1的质量比混合的混合填料。
偶联剂为硅烷偶联剂;防老剂为防老剂RD。
本实施例提供的电缆料的制备方法为:
按照质量份数,将密炼机预热至55℃,加入丁腈橡胶、天然橡胶和氯磺化聚乙烯,密炼处理10min,然后将高密度聚乙烯、马来酸酐接枝聚乙烯、催化交联剂和硫磺加入到密炼机中,以145℃的温度继续密炼6min,密炼结束后排料,混合料送入到烘箱中以170℃的温度高温硫化2h,然后自然冷却至室温,接着将混合料和填料、硬脂酸镁、增塑剂、偶联剂、防老剂一起投入到双螺杆挤出机中,以155℃的温度,300r/min的转速,经双螺杆挤出机混炼塑化并挤出造粒,得到所需电缆料。
实施例2
一种耐油耐热的高韧性电缆料,按照质量份数,电缆料的组分包括:丁腈橡胶60份,天然橡胶30份,高密度聚乙烯35份,氯磺化聚乙烯15份,马来酸酐接枝聚乙烯5份,催化交联剂4份,增塑剂6份,填料35份,硬脂酸镁3份,硫磺3份,偶联剂3份,防老剂2份。
其中,增塑剂为邻苯二甲酸二仲辛酯。
填料为钛白粉、轻质碳酸钙、氧化锌和MT炭黑按照5:4:2:1的质量比混合的混合填料。
偶联剂为硅烷偶联剂;防老剂为防老剂D。
本实施例提供的电缆料的制备方法为:
按照质量份数,将密炼机预热至65℃,加入丁腈橡胶、天然橡胶和氯磺化聚乙烯,密炼处理13min,然后将高密度聚乙烯、马来酸酐接枝聚乙烯、催化交联剂和硫磺加入到密炼机中,以150℃的温度继续密炼8min,密炼结束后排料,混合料送入到烘箱中以170℃的温度高温硫化3h,然后自然冷却至室温,接着将混合料和填料、硬脂酸镁、增塑剂、偶联剂、防老剂一起投入到双螺杆挤出机中,以165℃的温度,350r/min的转速,经双螺杆挤出机混炼塑化并挤出造粒,得到所需电缆料。
实施例3
一种耐油耐热的高韧性电缆料,按照质量份数,电缆料的组分包括:丁腈橡胶50份,天然橡胶28份,高密度聚乙烯32份,氯磺化聚乙烯12份,马来酸酐接枝聚乙烯4份,催化交联剂3.3份,增塑剂4.8份,填料33份,硬脂酸镁2.5份,硫磺2份,偶联剂2.1份,防老剂1.3份。
其中,增塑剂为邻苯二甲酸二环己酯。
填料为钛白粉、轻质碳酸钙、氧化锌和MT炭黑按照5:4:2:1的质量比混合的混合填料。
偶联剂为硅烷偶联剂;防老剂为防老剂264。
本实施例提供的电缆料的制备方法为:
按照质量份数,将密炼机预热至60℃,加入丁腈橡胶、天然橡胶和氯磺化聚乙烯,密炼处理12min,然后将高密度聚乙烯、马来酸酐接枝聚乙烯、催化交联剂和硫磺加入到密炼机中,以148℃的温度继续密炼7min,密炼结束后排料,混合料送入到烘箱中以170℃的温度高温硫化2.5h,然后自然冷却至室温,接着将混合料和填料、硬脂酸镁、增塑剂、偶联剂、防老剂一起投入到双螺杆挤出机中,以160℃的温度,330r/min的转速,经双螺杆挤出机混炼塑化并挤出造粒,得到所需电缆料。
性能测试
1、根据IEC 60811-1-1-1993《电缆绝缘和护套材料通用试验方法》中试验标准,对本实施例中电缆料的机械性能、电学性能和耐候性能进行检测,其中,选择上海帮塑国际贸易有限公司销售的美国陶氏8150型通用电线电缆料作为对照组,进行性能对比,测试实验结果如下:
表1:本实施例与对照组中电缆料的性能测试结果
分析以上实验数据发现,本发明提供的电缆料,其抗拉强度、断裂伸长率、均好于对照组的电缆料,因此可以认为本发明的电缆料具有更好的韧性和机械性能,该电缆料的体积电阻率略好于对照组,且具有很好的耐击穿性能,电学性能较好;此外,分析热老化试验发现,本发明提供的电缆料的耐热性能和抗老化性能也较为优秀。
2、测试本实施中电缆料和对照组电缆料的耐油和耐腐蚀性能,其中耐油性能通过油浸试验的吸油率进行测试,耐腐蚀性能通过盐雾试验后测试电缆料的拉伸强度变化率和断裂伸长率变化率来进行衡量:
表2:本实施例与对照组电缆料的耐油耐腐蚀性能测试
分析以上实验数据发现本发明的的电缆料经过油浸试验后,吸油率(即质量增长率)小于3.5%,而对照的电缆料的吸油率达到11.5%,对照组的电缆料的溶胀更为明显,因为可以认为,本发明的电缆料的耐油性更好,在重油环境中也不容易溶胀变性,可以具有更高的性能稳定性;而盐雾试验的结果表明,本发明提供的电缆料的耐腐蚀抗老化性能也好于对照组的电缆料。
以上所述仅为本发明的优选实施例而已,并不用于限制本发明,尽管参照前述实施例对本发明进行了详细的说明,对于本领域的技术人员来说,其依然可以对前述各实施例所记载的技术方案进行修改,或者对其中部分技术特征进行等同替换。凡在本发明的精神和原则之内,所作的任何修改、等同替换、改进等,均应包含在本发明的保护范围之内。
Claims (10)
1.一种耐油耐热的高韧性电缆料,其特征在于:按照质量份数,所述电缆料的组分包括:丁腈橡胶40-60份,天然橡胶25-30份,高密度聚乙烯30-35份,氯磺化聚乙烯8-15份,马来酸酐接枝聚乙烯3-5份,催化交联剂2-4份,增塑剂4-6份,填料30-35份,硬脂酸镁2-3份,硫磺1-3份,偶联剂1-3份,防老剂1-2份。
2.根据权利要求1所述的一种耐油耐热的高韧性电缆料,其特征在于:按照质量份数,所述电缆料的组分包括:丁腈橡胶48-55份,天然橡胶27-29份,高密度聚乙烯31-34份,氯磺化聚乙烯10-13份,马来酸酐接枝聚乙烯3.4-4.3份,催化交联剂2.5-3.7份,增塑剂4.5-5.6份,填料32-34份,硬脂酸镁2.4-2.8份,硫磺1.7-2.3份,偶联剂2-2.4份,防老剂1.2-1.5份。
3.根据权利要求2所述的一种耐油耐热的高韧性电缆料,其特征在于:按照质量份数,所述电缆料的组分包括:丁腈橡胶50份,天然橡胶28份,高密度聚乙烯32份,氯磺化聚乙烯12份,马来酸酐接枝聚乙烯4份,催化交联剂3.3份,增塑剂4.8份,填料33份,硬脂酸镁2.5份,硫磺2份,偶联剂2.1份,防老剂1.3份。
4.根据权利要求1所述的一种耐油耐热的高韧性电缆料,其特征在于,所述催化交联剂的制备方法包括如下步骤:
(1)按照质量份数,准备以下原料:超稳定Y型沸石45.5份,轻质二氧化硅15份,α-氧化铝18.3份,氧化锆3.7份,三辛基胺10.2份,羟丙基淀粉醚2.3份,去离子水200份,将以上物质混合均匀后配制成料浆,料浆以80-95℃的温度搅拌反应30-40min,然后经自然沉降后,过滤并烘干得到干粉;
(2)将干粉先送入到还原气氛的高温炉中,以450-600℃的温度煅烧1-2h,然后再送入到氧化气氛的高温炉中煅烧2-3h,煅烧结束后出窑,并自然冷却至室温,将75份产物送入到1000份1.2-1.5mol/L的氢氧化钾溶液中,浸渍搅拌,并以40-50℃的水浴温度处理1-1.5h,然后将分散液减压蒸发浓缩后,雾化干燥得到载体微粉;
(3)将12份还原性镁化合物,7.5份叔丁氧基铝,2.5份一氯二乙基铝加入到反应釜中,在氮气气氛的保护下,向反应釜内加入50份正辛烷溶剂和2份烷基糖苷,搅拌至分散均匀,然后将载体微粉加入,以110-120℃的温度保温加热反应1.5-2.5h;反应结束后将产物冷却至室温,过滤得到固形物;
(4)将钛酸丁酯、异丙醇、二亚乙基三胺、过氧化苯甲酰和α-氨基吡啶按照2:5:1:2:2的质量比,加入到10倍体积的二甲苯溶剂中,搅拌分散得到改性剂,然后将50份上步骤得到的固形物加入到150份改性剂中,搅拌分散反应45-60min,然后将产物过滤后,以150-160℃的温度烘干处理,得到所需催化交联剂。
5.根据权利要求4所述的一种耐油耐热的高韧性电缆料,其特征在于:所述步骤(2)中的高温炉内的还原气氛为氢气,氧化气氛为氧气。
6.根据权利要求4所述的一种耐油耐热的高韧性电缆料,其特征在于:所述步骤(3)中还原性镁化合物为二甲基镁、二丁基镁、丁基氯化镁和丁基乙氧基镁中的一种。
7.根据权利要求1所述的一种耐油耐热的高韧性电缆料,其特征在于:所述增塑剂为邻苯二甲酸二甲酯、邻苯二甲酸二丁酯、邻苯二甲酸二仲辛酯、邻苯二甲酸二环己酯、邻苯二甲酸二异壬酯和邻苯二甲酸二异癸酯中的一种。
8.根据权利要求1所述的一种耐油耐热的高韧性电缆料,其特征在于:所述填料为钛白粉、轻质碳酸钙、氧化锌和MT炭黑按照5:4:2:1的质量比混合的混合填料。
9.根据权利要求1所述的一种耐油耐热的高韧性电缆料,其特征在于:所述偶联剂为硅烷偶联剂;防老剂为防老剂RD、防老剂D或防老剂264。
10.根据权利要求1-9任意一项所述的一种耐油耐热的高韧性电缆料,其特征在于,所述电缆料的制备方法为:
按照质量份数,将密炼机预热至55-65℃,加入丁腈橡胶、天然橡胶和氯磺化聚乙烯,密炼处理10-13min,然后将高密度聚乙烯、马来酸酐接枝聚乙烯、催化交联剂和硫磺加入到密炼机中,以145-150℃的温度继续密炼6-8min,密炼结束后排料,混合料送入到烘箱中以170℃的温度高温硫化2-3h,然后自然冷却至室温,接着将混合料和填料、硬脂酸镁、增塑剂、偶联剂、防老剂一起投入到双螺杆挤出机中,以155-165℃的温度,300-350r/min的转速,经双螺杆挤出机混炼塑化并挤出造粒,得到所需电缆料。
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