CN105131413B - 高强度耐高温硅烷交联电缆用半导电屏蔽料及其制备方法 - Google Patents
高强度耐高温硅烷交联电缆用半导电屏蔽料及其制备方法 Download PDFInfo
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Abstract
本发明涉及高强度耐高温硅烷交联电缆用半导电屏蔽料及其制备方法，按质量份计，原料包括：EVA 100份，导电炭黑25～35份，POE 8～12份，改性助剂2～3份，抗氧剂2～3份，增塑剂4～7份，对羟基苯磺酸0.5～2份，其中POE为硅烷交联的POE。于密炼机内，将EVA、导电炭黑、POE、抗氧剂、增塑剂混合均匀，于50～60℃进行初次密炼，然后由单螺杆挤出，再加入改性助剂和对羟基苯磺酸，进行二次密炼，熟胶由双螺杆挤出，造粒和风干，即获得半导电屏蔽料。屏蔽料所获得的电缆成品在低温环境下的强韧度得到了提高，同时电缆亦具有更好的耐高温性能。
Description
技术领域
本发明涉及一种高强度、耐高温的电缆用半导电屏蔽料和其制备方法。
背景技术
欧盟的ROHS指令的实施以后，明确规定了将严格地限制六种有害物质在电子电气设备中的使用，尽管PVC电线电缆还没有完全限制，但是全球无卤化的电线电缆的需求不断增大，而高品质的无卤阻燃环境友好的电缆料的开发将是一个新的课题。
乙烯（丙烯）-α-烯烃共聚物的新型热塑性弹性体——聚烯烃弹性体(Polyolefinelastomer，简称POE）分子链饱和，属于非极性材料，因此具有良好的电气绝缘、耐氧、耐臭氧以及耐高温老化性，这些性能都非常适合应用于电缆的护套材料，因此POE 可以作为电缆的包覆材料，有很大的市场需求和应用前景。
目前，当环境温度降低至10℃以下后，电缆外皮容易脆化出现破损的情况，提高电缆的强度使适应低温工作环境是本领域技术人员需要思考的问题。另外，对于负载大的电缆，高压输电时电缆周围电场大，一定时间累积下来会形成工作高温，现有电缆的耐高温值只有70℃，无法适应目前远距离高压电传送，提高电缆的耐高温性能也是亟待解决的难题之一。
发明内容
本发明所要解决的技术问题是针对上述现有技术提供一种电缆用半导电电缆屏蔽料，提高电缆成品的强韧性，尤其是在低温环境下的强韧度，并使电缆同时具有更好的耐高温性能。
本发明解决上述问题所采用的技术方案为：一种高强度耐高温硅烷交联电缆用半导电屏蔽料，由如下质量份的原料制备而成：
EVA 100份，导电炭黑25～35份，POE 8～12份，改性助剂2～3份，抗氧剂2～3份，增塑剂4～7份，对羟基苯磺酸0.5～2份，其中POE为硅烷交联的POE。
优选地，所述改性助剂为PP或PC，改善POE与基料EVA的相容性，本发明所选用的PP或PC（聚碳酸酯）化学稳定性好，可使改性的最终屏蔽料具有耐高温、耐老化、耐辐射和耐磨等特点。
优选地，所述抗氧剂为芳香胺类抗氧剂或受阻酚类抗氧剂，抑制氧对聚合物的氧化，提高耐候性，延长电缆产品的使用寿命。芳香胺类抗氧剂包括二苯胺、对苯二胺和二氢喹啉及其衍生物或聚合物；受阻酚类抗氧剂包括2，6-三级丁基-4-甲基苯酚、双(3，5-三级丁基-4-羟基苯基)硫醚、四（β-(3，5-三级丁基-4-羟基苯基)丙酸）季戊四醇酯。。
在EVA屏蔽料加工过程中，屏蔽料同加工机械之间以及原料大分子之间存在相互摩擦，会产生一定的摩擦热，摩擦热过大会造成材料难以加工甚至产生焦烧。而且，屏蔽料中炭黑的添加量较大，本发明增塑剂优选白油、石蜡、硬脂酸、硬脂酸锌、聚乙烯蜡中的一种或两种以上，在加工时增加密炼机中混合物的润滑性，便于加工，并且使成品柔韧性得到增强。
进一步地，上述POE中辛烯的质量含量为20～30%，密度为0.88±0.015g/cm3,作为EVA的改性添加剂，能够提高电缆的强度、弹性和伸长率，尤其是耐低温性能，使电缆材料适于在低温环境下使用，不易发生低温脆裂。
进一步地，所述硅烷交联的POE所使用的硅烷交联剂的型号为KH-560、KH570或KH-151，使用浓度为0.5～6（wt）%，以乙醇的水溶液作为溶剂，乙醇和水以1:6～12的体积比混合，并于溶液中添加0.05～0.75（wt）%的丙烯酸或者2-羟基丁二酸。硅烷交联可形成束状结构，提高耐热性和电性能，对电缆耐高温性能的提高有利，通过对硅烷偶联剂的选择和硅烷使用浓度等交联因素控制硅烷交联点间的距离，于POE改性低温性能好坏有重要影响。在硅烷偶联剂的相应改性溶液中添加丙烯酸或2-羟基丁二酸，一方面作为水解反应的催化剂，另一方面也能够调节硅烷交联点，使长链分子间的空间网状结构交联点分布均匀，分子间的间隔均匀、间距合理，避免交联结构本身构成POE支链的空间限制位阻，为POE的支链预留出弹性活动空间，为保障最终电缆产品的柔韧性提供微观结构上的调剂。
制造上述高强度耐高温硅烷交联电缆用半导电屏蔽料的方法：于密炼机内，将EVA、导电炭黑、POE、抗氧剂、增塑剂混合均匀，于50～60℃进行初次密炼，然后由单螺杆挤出，再加入改性助剂和对羟基苯磺酸，进行二次密炼，熟胶由双螺杆挤出，造粒和风干，即获得半导电屏蔽料。
与现有技术相比，本发明的优点在于：本发明以硅烷交联的POE改性EVA基料，经硅烷偶联剂接枝后的POE与EVA发生水解缩合反应，形成三维网状结构的交联POE/EVA，该微观结构体现在宏观上是使材料的强度和耐高温型得到显著改善，提高电缆成品的强韧性，扩宽了电缆的适应温度范围，尤其使电缆能够适应10℃以下的低温环境，不易发生低温脆破损，并且耐高温性能最高温度达到150℃。
再来，在原料中添加PP或PC作为改性助剂，增高POE和EVA的相容性，优化改性效果，提高电缆材料的化学稳定性，在炼胶过程中降低混胶的玻璃化温度，有助于提高电缆产品的低温韧性。进一步地，在原料中添加对羟基苯磺酸使原料中的主要大分子之间发生不可逆的链接反应，提高电缆的耐冲击强度，尤其是电缆的表面强度，受外力状态下如承压或牵引，不易破损划花。
具体实施方式
以下结合实施例对本发明作进一步详细描述。
实施例1
本实施例中电缆用半导电屏蔽料由一下重量份的原料制备而成，EVA 100份，导电炭黑30份，POE 10份，PP（聚丙烯，数均分子量为80000～120000）3份，对苯二胺3份，硬脂酸5份，对羟基苯磺酸1份，其中POE为硅烷接枝的POE， POE中辛烯的质量含量为20～30%，密度为0.88±0.015g/cm3，所用硅烷偶联剂为γ—（2，3-环氧丙氧）丙基三甲氧基硅烷，硅烷偶联剂的使用浓度为1.2（wt）%，以乙醇的水溶液作为溶剂，乙醇和水以1:8的体积比混合，并于溶液中再添加0.25（wt）%的丙烯酸。
屏蔽料的制备方法为，于密炼机内，将EVA、导电炭黑、硅烷交联的POE、对苯二胺、硬脂酸混合均匀，于50～60℃进行初次密炼，然后由单螺杆挤出，再加入PP和对羟基苯磺酸，进行二次密炼，熟胶由双螺杆挤出，造粒和风干，即获得半导电屏蔽料。
实施例2
本实施例中电缆用半导电屏蔽料由一下重量份的原料制备而成，EVA 100份，导电炭黑32份，POE 8份，PC（聚碳酸酯，数均分子量为15000～25000）3份，2，6-三级丁基-4-甲基苯酚2份，白油6份，对羟基苯磺酸1份，其中POE为硅烷接枝的POE， POE中辛烯的质量含量为20～30%，密度为0.88±0.015g/cm3，所用硅烷偶联剂为γ—（甲基丙烯酰氧）丙基三甲氧基硅烷，硅烷偶联剂的使用浓度为2.0（wt）%，以乙醇的水溶液作为溶剂，乙醇和水以1:6的体积比混合，并于溶液中添加0.35（wt）%的2-羟基丁二酸。
屏蔽料的制备方法为，于密炼机内，将EVA、导电炭黑、硅烷交联的POE、2，6-三级丁基-4-甲基苯酚、白油混合均匀，于50～60℃进行初次密炼，然后由单螺杆挤出，再加入PC和对羟基苯磺酸，进行二次密炼，熟胶由双螺杆挤出，造粒和风干，即获得半导电屏蔽料。
实施例3
本实施例中电缆用半导电屏蔽料由一下重量份的原料制备而成，EVA 100份，导电炭黑32份，POE 8份，PC 2份，二苯胺 3份，聚乙烯蜡和石蜡的混合物 5份，对羟基苯磺酸1份，其中POE为硅烷接枝的POE， POE中辛烯的质量含量为20～30%，密度为0.88±0.015g/cm3，所用硅烷偶联剂为乙烯基三乙氧基硅烷，硅烷偶联剂的使用浓度为0.5（wt）%，以乙醇的水溶液作为溶剂，乙醇和水以1:10的体积比混合，并于溶液中添加0.3（wt）%的2-羟基丁二酸。
屏蔽料的制备方法为，于密炼机内，将EVA、导电炭黑、硅烷交联的POE、二苯胺、聚乙烯蜡和石蜡的混合物混合均匀，于50～60℃进行初次密炼，然后由单螺杆挤出，再加入PC和对羟基苯磺酸，进行二次密炼，熟胶由双螺杆挤出，造粒和风干，即获得半导电屏蔽料。
实施例4
本实施例中电缆用半导电屏蔽料由一下重量份的原料制备而成，EVA 100份，导电炭黑30份，POE 10份，PP（聚丙烯，数均分子量为80000～120000）2份，双(3，5-三级丁基-4-羟基苯基)硫醚2份，硬脂酸锌4份，对羟基苯磺酸1份，其中POE为硅烷接枝的POE，POE中辛烯的质量含量为20～30%，密度为0.88±0.015g/cm3，所用硅烷偶联剂为γ—（2，3-环氧丙氧）丙基三甲氧基硅烷，硅烷偶联剂的使用浓度为4（wt）%，以乙醇的水溶液作为溶剂，乙醇和水以1:8的体积比混合，并于溶液中添加0. 5（wt）%的丙烯酸。
屏蔽料的制备方法为，于密炼机内，将EVA、导电炭黑、硅烷交联的POE、双(3，5-三级丁基-4-羟基苯基)硫醚、硬脂酸锌混合均匀，于50～60℃进行初次密炼，然后由单螺杆挤出，再加入PP和对羟基苯磺酸，进行二次密炼，熟胶由双螺杆挤出，造粒和风干，即获得半导电屏蔽料。
上述各实施例所得半导电屏蔽料所制备的电缆，具有如下性能指标：
拉伸强度≥10MPa，断裂伸长率≥200%，密度≤3g/cm3，热延伸长率≤100%，冷却后永久变形≤15%，空气热老化实验拉伸强度变化率≤±20%。
本发明具有光滑的电缆表面，电缆绝缘层无残留物，耐温性能优良，最高适用温度达150℃，并且适应低温环境下（10℃以下）适用，抗拉强度达20MPa，电缆表面强度高，不易磨损。使用本产品制造电缆可以长时间连续开机生产，不但节约能源和材料，而且电缆质量稳定，使用寿命长。
Claims (7)
1.一种高强度耐高温硅烷交联电缆用半导电屏蔽料，其特征在于：由如下质量份的原料制备而成：
EVA 100份，导电炭黑25～35份，POE 8～12份，改性助剂2～3份，抗氧剂2～3份，增塑剂4～7份，对羟基苯磺酸0.5～2份，其中POE为硅烷交联的POE；
所述硅烷交联的POE所使用的硅烷交联剂的型号为KH570或KH-151，使用浓度为0.5～6wt%，以乙醇的水溶液作为溶剂，乙醇和水以1:6～12的体积比混合，并于溶液中添加0.05～0.75wt%的丙烯酸或者2-羟基丁二酸；
或者所述硅烷交联的POE所使用的硅烷交联剂的型号为KH-560，使用浓度为0.5～6wt%，以乙醇的水溶液作为溶剂，乙醇和水以1:6～12的体积比混合，并于溶液中添加0.05～0.75wt%的丙烯酸。
2.根据权利要求1所述的高强度耐高温硅烷交联电缆用半导电屏蔽料，其特征在于：所述改性助剂为PP或PC。
3.根据权利要求1所述的高强度耐高温硅烷交联电缆用半导电屏蔽料，其特征在于：所述抗氧剂为芳香胺类抗氧剂或受阻酚类抗氧剂。
4.根据权利要求3所述的高强度耐高温硅烷交联电缆用半导电屏蔽料，其特征在于：所述芳香胺类抗氧剂包括二苯胺、对苯二胺和二氢喹啉及其衍生物或聚合物，所述受阻酚类抗氧剂包括2，6-三级丁基-4-甲基苯酚、双(3，5-三级丁基-4-羟基苯基)硫醚、四（β-(3，5-三级丁基-4-羟基苯基)丙酸）季戊四醇酯。
5.根据权利要求1所述的高强度耐高温硅烷交联电缆用半导电屏蔽料，其特征在于：所述增塑剂为白油、石蜡、硬脂酸、硬脂酸锌、聚乙烯蜡中的一种或两种以上。
6.根据权利要求1所述的高强度耐高温硅烷交联电缆用半导电屏蔽料，其特征在于：所述POE中辛烯的质量含量为20～30%。
7.一种制造权利要求1所述高强度耐高温硅烷交联电缆用半导电屏蔽料的方法，其特征在于：于密炼机内，将EVA、导电炭黑、POE、抗氧剂、增塑剂混合均匀，于50～60℃进行初次密炼，然后由单螺杆挤出，再加入改性助剂和对羟基苯磺酸，进行二次密炼，熟胶由双螺杆挤出，造粒和风干，即获得半导电屏蔽料。
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