CN106398037B - 电缆用的阻燃包覆组合物 - Google Patents

电缆用的阻燃包覆组合物 Download PDF

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CN106398037B
CN106398037B CN201610793030.1A CN201610793030A CN106398037B CN 106398037 B CN106398037 B CN 106398037B CN 201610793030 A CN201610793030 A CN 201610793030A CN 106398037 B CN106398037 B CN 106398037B
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许彬冰
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Abstract

本发明提供了一种电缆用的阻燃包覆组合物，包含：基础树脂和阻燃抑烟剂，其中所述阻燃抑烟剂为

Description

电缆用的阻燃包覆组合物
技术领域
本发明涉及电缆领域，更具体为电缆用的阻燃包覆组合物。
背景技术
为了减少火灾的发生和发展，人们对电线电缆的阻燃低烟化进行了种种探讨。实现电缆材料的阻燃、低烟、耐热的最佳措施是选择本身具备这些特性的聚合物材料。PVC树脂则因其具有极高的电绝缘性(例如耐电击穿，可用于1万伏低压电缆)、较耐老化、具有化学稳定性、耐磨性且价格低廉等优点而成为目前用量最大的电缆材料原料。我国每年生产的PVC树脂中约有20％用于电缆材料。但是PVC树脂燃烧时释放出氯化氢、一氧化碳、二氧化碳、各种芳香烃类、含氯化合物等有毒有害气体。由于火灾发生时烟气在建筑物中水平方向流速约为0.3-0.8m/s；垂直方向的流速约为2-4m/s，因此短时间内有毒烟气就会充满整个建筑物中，给人员疏散及消防救援工作带来极大的困难。统计数据表明，在火灾中，烟是最先产生和最易致死且贻误救火时机的因素，据统计，火灾中的死亡人数有85％是窒息所致，所以“抑烟”与“阻燃”是相提并论的，甚至对PVC而言，“抑烟”比“阻燃”更为重要。
对阻燃抑烟剂的主要要求是:(1)体系中的含卤量应控制在一定水平以下，且阻燃抑烟效果好；(2)满足不同级别和适用场合的产品；(3)能通过表面处理技术、高分散技术实现与聚合物间较好的相容性；(4)不损伤聚合物阻燃材料的物理机械性能，尽可能降低阻燃剂用量和成本；(5)现代阻燃抑烟剂不应仅仅局限于提高阻燃抑烟性，还应在生产、使用周期甚至是回收利用或焚烧环节表现出优良的性能，如高热稳定性、低毒性，以免后期产品回收时损失制品原有性能或产生多溴代苯并恶英/吠喃(PBDDIF)等有毒物质。总之，阻燃抑烟剂最终要能有效提高体系的氧指数，降低烟密度；增加成炭量；使热解产物中芳香族挥发分比例减少，脂肪族挥发分比例增加；且不影响聚合物材料的回收利用。
目前应用于PVC的阻燃剂主要有卤-锑协同阻燃剂、磷酸酯类阻燃剂、无机阻燃抑烟剂等。虽然这些阻燃剂己经实现了工业化，但仍然存在诸如阻燃抑烟剂用量大、生产成本高、产品回收再用率低及产品环境健康效应不佳等问题，尤其PVC自身极高的含氯量和PVC结构中的难以克服的缺陷使得新型高效阻燃抑烟剂的研发一直是PVC科研工作者的难点。因此，如何改善阻燃剂对PVC等基体树脂材料机械性能的不良影响、降低其生产成本等仍然是需要解决的问题。
发明内容
为了解决上述问题，发明人进行积极的研究，结果他们发现一种新型的阻燃抑烟剂，通过将这种阻燃抑烟剂与基体树脂、其他添加剂等联合使用能够得到阻燃性能、力学性能、耐高温性能优良的阻燃包覆组合物。
在一个方面中，本发明提供了一种电缆用的阻燃包覆组合物，包含：
基础树脂和阻燃抑烟剂，其中所述阻燃抑烟剂为
并且相对于每100重量份的所述基础树脂，所述阻燃抑烟剂的用量为5-30重量份。
优选地，本发明所述的阻燃包覆组合物还包含增塑剂、热稳定剂、抗氧剂和润滑剂，其中相对于每100重量份的所述基础树脂，所述增塑剂的用量为5-60重量份，所述热稳定剂的用量为1-30重量份，所述抗氧剂的用量为0.1-10重量份并且所述润滑剂的用量为0.1-5重量份。
更优选地，其中所述基础树脂包含三元乙丙橡胶、聚氯乙烯、甲基乙烯基硅橡胶、硅橡胶/层状硅酸盐纳米复合材料、聚氨酯、聚酯或其任意的组合。
更优选地，所述的层状硅酸盐选自蒙脱土、C16BrN改性的有机蒙脱土、泥灰石、高岭土、滑石、云母、纤蛇蚊石或其任意组合。
更优选地，其中所述甲基乙烯基硅橡胶还包含气相白炭黑。
优选地，阻燃包覆组合物还包含增塑剂、热稳定剂、抗氧剂和润滑剂。相对于每100重量份的所述基础树脂，所述增塑剂的用量为5-60重量份，所述热稳定剂的用量为1-30重量份，所述抗氧剂的用量为0.1-10重量份并且所述润滑剂的用量为0.1-5重量份。
增塑剂可以包括邻苯二甲酸二(2-乙基己)酯(DOP)、邻苯二甲酸二正辛酯(DNOP或DnOP)、邻苯二甲酸丁苄酯(BBP)、邻苯二甲酸二仲辛酯(DCP)、邻苯二甲酸二环己酯(DCHP)、邻苯二甲酸二丁酯(DBP)、邻苯二甲酸二异丁酯(DIBP)等。热稳定剂可以包括碱式铅盐、金属皂、有机锡、环氧化合物、亚磷酸酯、多元醇等。优选三盐基硫酸铅(TBLS)。抗氧剂可以包括硫酚类、双酚A等。润滑剂包括滑石粉、有机酸(例如硬脂酸)等。
优选的，基础树脂包含三元乙丙橡胶、聚氯乙烯、甲基乙烯基硅橡胶(MVMQ)、硅橡胶/层状硅酸盐纳米复合材料、聚氨酯、聚酯或其任意的组合。
特别优选的是MVMQ。MVMQ的化学结构为
这种低不饱和度的分子结构使硅橡胶具有优良的耐热老化性、耐候性及耐紫外线和臭氧侵蚀，同时大大提高了硫化活性，提高硫化胶的交联效率，从而可以减少硫化剂用量。当温度变化时，分子之间的作用力改变很少，因而可以在相当宽的温度范围内(-70-250℃)保持橡胶弹性。此外，硅原子上带有有机基团，使其分子链的对称性下降，从而使其结晶温度和玻璃化温度降低。MVMQ具有中等的耐辐照射性能，能吸收达((4.0-5.0)X 103Gy的辐照剂量。
还优选使用硅橡胶/层状硅酸盐纳米复合材料，例如MVMQ/C16BrN改性的有机蒙脱土。优选的，层状硅酸盐选自蒙脱土、C16BrN改性的有机蒙脱土、泥灰石、高岭土、滑石、云母、纤蛇蚊石或其任意组合。
聚合物/粘土纳米复合材料的出现为阻燃技术开辟了新的领域，被誉为“阻燃材料技术革命”。将阻燃体系与纳米级无机物结合使用，能够提高材料的燃烧性能同时改善其物理机械性能。例如，改性蒙脱土/硅橡胶纳米复合材料具有优异的机械性能和阻燃性。还可以用白炭黑将所述复合材料补强。
总之，本发明的阻燃包覆组合物可以用于各种电线电缆，能够表现出优良的阻燃性能和机械性能的平衡。特别是，纳米级羟基锡酸锌是一种新型的阻燃剂，能够单独使用或者与各种其他的阻燃剂混合使用，起到增强阻燃效果的作用。
具体实施方式
以下将描述实施本发明的实施方案。然而，本发明的范围不局限于所述的实施方式，只要不损害主旨，可以对本发明进行各种更改。除非另有说明，否则以下的比例和％分别是指重量比和重量％。
实施例1阻燃包覆组合物的制备
阻燃包覆组合物的基本配方如下表所示：
将上述各组分混合均匀后，在双辊机上熔融共混，开炼温度为160-170℃，开炼l0min；而后在165-170℃用平板硫化机上将制备的阻燃包覆材料热压成为l0X10X3(mm3)，l0X 0l0X2(mm3)，l0mmx l0X1(mm3)的平板、或用切片机按照标准切成型后用于各种测试。
实施例2
按照上述相同的方法制备阻燃包覆组合物2，其中不添加阻燃抑烟剂。
极限氧指数(LOI)测试
HC-2型氧指数测定仪，江宁分析仪器厂。将样品加工成100mmx6.5mmx3.0mm3样条，按照GB/T2406-96(塑料燃烧性能试验方法-氧指数法)测定样品氧指数。
实施例1的阻燃包覆组合物的LOI为38.6，实施例2的阻燃包覆组合物的LOI为13.1。

Claims (5)

1.一种电缆用的阻燃包覆组合物，包含：
基础树脂和阻燃抑烟剂，其中所述阻燃抑烟剂为
并且相对于每100重量份的所述基础树脂，所述阻燃抑烟剂的用量为5-30重量份。
2.根据权利要求1所述的阻燃包覆组合物，还包含增塑剂、热稳定剂、抗氧剂和润滑剂，其中相对于每100重量份的所述基础树脂，所述增塑剂的用量为5-60重量份，所述热稳定剂的用量为1-30重量份，所述抗氧剂的用量为0.1-10重量份并且所述润滑剂的用量为0.1-5重量份。
3.根据权利要求1或2所述的阻燃包覆组合物，其中所述基础树脂包含三元乙丙橡胶、聚氯乙烯、甲基乙烯基硅橡胶、硅橡胶/层状硅酸盐纳米复合材料、聚氨酯、聚酯或其任意的组合。
4.根据权利要求3所述的阻燃包覆组合物，其中，所述的层状硅酸盐选自蒙脱土、C16BrN改性的有机蒙脱土、泥灰石、高岭土、滑石、云母、纤蛇蚊石或其任意组合。
5.根据权利要求3所述的阻燃包覆组合物，其中所述甲基乙烯基硅橡胶还包含气相白炭黑。
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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101143944A (zh) * 2006-09-13 2008-03-19 中国石油天然气股份有限公司 一种聚乙烯用无卤膨胀型阻燃剂
CN104356538A (zh) * 2014-10-28 2015-02-18 宁波一舟塑胶有限公司 一种阻燃消烟的聚氯乙烯电线电缆料
CN104403227A (zh) * 2014-11-14 2015-03-11 宁波一舟塑胶有限公司 一种仿硅胶阻燃聚氯乙烯塑料

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101143944A (zh) * 2006-09-13 2008-03-19 中国石油天然气股份有限公司 一种聚乙烯用无卤膨胀型阻燃剂
CN104356538A (zh) * 2014-10-28 2015-02-18 宁波一舟塑胶有限公司 一种阻燃消烟的聚氯乙烯电线电缆料
CN104403227A (zh) * 2014-11-14 2015-03-11 宁波一舟塑胶有限公司 一种仿硅胶阻燃聚氯乙烯塑料

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