CN105801996B - 一种阻燃高导热护套材料及其制备和应用 - Google Patents

一种阻燃高导热护套材料及其制备和应用 Download PDF

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CN105801996B
CN105801996B CN201610210769.5A CN201610210769A CN105801996B CN 105801996 B CN105801996 B CN 105801996B CN 201610210769 A CN201610210769 A CN 201610210769A CN 105801996 B CN105801996 B CN 105801996B
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吴新锋
唐波
彭熙瑜
郑德峰
吕永根
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Abstract

本发明涉及一种阻燃高导热护套材料及其制备和应用，所述阻燃高导热护套材料的原料组分包括：乙烯‑辛烯共聚物100份，膨胀石墨10‑30份，氮化铝微粉30‑100份，偶联剂0.5‑3份，多烯基辐照敏化剂0.5‑3份，抗氧剂0.5份，增塑剂0.5份，热稳定剂0.5份，色母粒2‑5份。制备原料进行混合，搅拌，原料不超过60℃；然后在双螺杆挤出机中挤出，拉丝，水冷，风冷，造粒，即得。应用：在电缆护套材料中的应用。本发明制备工艺快速，而且辐照交联后的护套具有非常优越的阻燃性能、拉伸强度和导热性能，氧指数可以达到30以上，拉伸强度不小于5MPa，导热系数提高50％以上。

Description

一种阻燃高导热护套材料及其制备和应用
技术领域
本发明属于护套材料及其制备和应用领域，特别涉及一种阻燃高导热护套材料及其制备和应用。
背景技术
高分子材料常规的阻燃方法是添加各种阻燃剂进行阻燃，但随着对高性能、高效、环境友好聚合物阻燃体系要求的提高，阻燃评价方法的不断完善和更加科学，以及世界各国阻燃法规的日趋严格，特别是欧盟两项指令“废弃电子电器设备指令"(West Electricaland Electronic Equipment Directive，WEEE)(2003年3月生效)及“电子电器设备中禁用有害物质指令”(Restriction of Hazardous Substances Directive，RoHS)的颁布，使得传统的卤素等阻燃体系受到了严峻的挑战。新型阻燃剂要求材料不仅要有较高的阻燃效率，还要求阻燃剂不易渗出，且本身无毒或低毒，另外还要求原材料来源广泛。现阶段的金属氧化物如氢氧化镁或者氢氧化铝因为其填充量大即阻燃效率低而受到限制，新型阻燃高分子材料发展的方向要求阻燃体系不仅具有良好的阻燃性能，而膨胀型阻燃剂恰逢其时，满足上述要求。同时应该注意到材料燃烧的三要素：燃料、空气、热量。如果能把电发热产生热量及时地导出，也可以提高材料的导热性能。
发明内容
本发明所要解决的技术问题是提供一种阻燃高导热护套材料及其制备方法，本发明的辐照交联阻燃电缆护套具有优越的阻燃性能，氧指数可以达到30以上，同时导热系数可以比纯料提高50％以上，低烟，且力学性能，耐酸碱性，耐水性等性能优越。
本发明的一种阻燃高导热护套材料，其特征在于：按重量份数计，所述阻燃高导热护套材料的原料组分包括：乙烯-辛烯共聚物100份，膨胀石墨10-30份，氮化铝微粉30-100份，偶联剂0.5-3份，多烯基辐照敏化剂0.5-3份，抗氧剂0.5份，增塑剂0.5份，稳定剂0.5份，色母粒2-5份。
所述乙烯-辛烯共聚物的技术参数为熔融指数≤2g/10min(ASTM D-1238，190℃，2.16kg)，门尼粘度ML1+4(121℃)为24±4，密度0.88g/cm3。
所述膨胀石墨为内部插层硫酸的石墨，粒径为100-300μm，其膨胀倍数为200倍-500倍。
膨胀石墨的制备方法：100-300μm的鳞片石墨(100g)放入含有浓硫酸(50g)和重铬酸钾(50g)的三口烧瓶中，在35℃水浴内，搅拌30min，待反应完成后，将产品进行抽滤，并用去离子水洗涤至中性，并将产品在60℃条件下干燥30min，干燥后的产品即为可膨胀石墨。
所述氮化铝微粉的颗粒大小为3-10μm；偶联剂为硅烷偶联剂KH550。氮化铝微粉需要和偶联剂KH550进行复配使用。
所述多烯基辐照敏化剂为二乙二醇二甲基丙烯酸酯DEGDMA，三丙二醇二甲基丙烯酸酯TPGDMA，邻苯二甲酸三乙二醇二丙烯酸酯PTDMA，三羟甲基丙烷三甲基丙烯酸酯TMPTMA中的一种或几种。
所述抗氧剂为抗氧剂1010，也可以为其它类型的抗氧剂。
所述增塑剂为己二酸二癸酯，不限于本物质；
所述稳定剂为硬脂酸锌，不限于本物质。
本发明的一种如权利要求1-7任一所述的阻燃高导热护套材料的制备方法，包括：将原料进行混合，搅拌，原料不超过60℃；然后在双螺杆挤出机中挤出，拉丝，水冷，风冷，造粒，即得阻燃高导热护套材料。
所述搅拌速率为500-800rpm，搅拌时间为3-8min。
所述双螺杆挤出机中挤出的温度为180℃。
本发明的一种阻燃高导热护套材料的应用，用于交联阻燃电缆护套材料的制备，包括：阻燃高导热护套材料和电缆材料共混挤出后进行辐照交联，即得交联阻燃电缆护套材料辐照交联为：高能电子加速器下常温进行辐照交联，辐照剂量为50-80kGy。
所述电子加速器型号为GJ-2E-EB，2MeV，10mA。
经过共混挤出成线后，在电子加速器下辐照50-80kGy即可以快速交联，且材料不像过氧化物交联那样会有很多的气泡产生。
本发明把膨胀阻燃剂膨胀石墨和导热填料微米氮化铝相结合的方式制备出膨胀阻燃的阻燃高导热护套材料，同时利用辐照交联的方法制备出交联护套材料。
本发明所使用的膨胀石墨价格便宜，阻燃效率高，可以很好的应用于电缆护套材料。且辐照成型过程中材料不会出现气泡，成型速度快。本发明使用的氮化铝微米颗粒导热系数高。
有益效果
(1)本发明的辐照交联阻燃电缆护套材料具有无卤、低烟、低毒、环保等特点，且价格低廉；
(2)本发明的辐照交联阻燃电缆护套材料制备方法工艺快速，且辐照成型过程中材料不会出现气泡；
(3)本发明的辐照交联阻燃电缆护套具有优越的阻燃性能，氧指数可以达到30以上，同时导热系数可以比纯料提高50％以上，低烟，且力学性能，耐酸碱性，耐水性等性能优越。
具体实施方式：
下面结合具体实施例，进一步阐述本发明。应理解，这些实施例仅用于说明本发明而不用于限制本发明的范围。此外应理解，在阅读了本发明讲授的内容之后，本领域技术人员可以对本发明作各种改动或修改，这些等价形式同样落于本申请所附权利要求书所限定的范围。
实施例1
取(以重量计)乙烯-辛烯共聚物(100份)，膨胀石墨(10份)，氮化铝微粉(30份)，硅烷偶联剂KH550(0.5份)，多烯基辐照敏化剂DEGDMA(2份)，抗氧剂(0.5份)，增塑剂(0.5份)，稳定剂(0.5份)，色母粒(2份)依次放入高速混合机中高速搅拌5min后(500转/min)，物料不超过60℃。取出物料放入双螺杆挤出机中挤出，拉丝，水冷，风冷，造粒即获得辐照交联阻燃电缆护套材料母料。挤出温度为180℃。以上护套母料和电缆材料共挤出后，在高能电子加速器(GJ-2E-EB,2MeV,10mA)下常温辐照交联，辐照剂量为80kGy，即可获得辐照交联阻燃高导热护套。
实施例2
取(以重量计)乙烯-辛烯共聚物(100份)，膨胀石墨(20份)，氮化铝微粉(50份)，硅烷偶联剂KH550(1份)，多烯基辐照敏化剂TMPTMA(2份)，抗氧剂(0.5份)，增塑剂(0.5份)，稳定剂(0.5份)，色母粒(2份)依次放入高速混合机中高速搅拌5min后(500转/min)，物料不超过60℃。取出物料放入双螺杆挤出机中挤出，拉丝，水冷，风冷，造粒即获得辐照交联阻燃电缆护套材料母料。挤出温度为180℃。以上护套母料和电缆材料共挤出后，在高能电子加速器(GJ-2E-EB,2MeV,10mA)下常温辐照交联，辐照剂量为80kGy，即可获得辐照交联护套。
实施例3
取(以重量计)乙烯-辛烯共聚物(100份)，膨胀石墨(30份)，氮化铝微粉(80份)，硅烷偶联剂KH550(1.5份)，多烯基辐照敏化剂PTDMA(2份)，抗氧剂(0.5份)，增塑剂(0.5份)，稳定剂(0.5份)，色母粒(2份)依次放入高速混合机中高速搅拌5min后(500转/min)，物料不超过60℃。取出物料放入双螺杆挤出机中挤出，拉丝，水冷，风冷，造粒即获得辐照交联阻燃电缆护套材料母料。挤出温度为180℃。以上护套母料和电缆材料共挤出后，在高能电子加速器(GJ-2E-EB,2MeV,10mA)下常温辐照交联，辐照剂量为80kGy，即可获得辐照交联高阻燃导热护套。
产品性能检测：
将上述实施例1-3中的材料利用电缆切片机切片后进行极限氧指数(ASTM D2386-97)、拉伸性能(ASTM D638-91)导热系数(ASTM E1461)等性能的测试(测试标准进行补充)。结果显示：实施例1、2、3中氧指数测试也表明材料氧指数依次增加到30、31和31.5，且力学性能分别为7.5MPa、6.3MPa和5.7MPa，且导热性能分别为0.45W/(mK)，0.75W/(mK)和1.1W/(mK)，完全满足护套材料的要求。

Claims (8)

1.一种阻燃高导热护套材料，其特征在于：按重量份数计，所述阻燃高导热护套材料的原料组分包括：乙烯-辛烯共聚物100份，膨胀石墨10-30份，氮化铝微粉30-100份，偶联剂0.5-3份，多烯基辐照敏化剂0.5-3份，抗氧剂0.5份，增塑剂0.5份，热稳定剂0.5份，色母粒2-5份；其中，多烯基辐照敏化剂为二乙二醇二甲基丙烯酸酯DEGDMA，三丙二醇二甲基丙烯酸酯TPGDMA，邻苯二甲酸三乙二醇二丙烯酸酯PTDMA中的一种或几种；氮化铝微粉的颗粒大小为3-10μm。
2.根据权利要求1所述的一种阻燃高导热护套材料，其特征在于：所述膨胀石墨为内部插层硫酸的石墨，粒径为100-300μm，其膨胀倍数为200倍-500倍。
3.根据权利要求1所述的一种阻燃高导热护套材料，其特征在于：所述偶联剂为硅烷偶联剂KH550。
4.根据权利要求1所述的一种阻燃高导热护套材料，其特征在于：所述抗氧剂为抗氧剂1010；增塑剂为己二酸二癸酯；热稳定剂为硬脂酸锌。
5.一种如权利要求1-4任一所述的阻燃高导热护套材料的制备方法，包括：将原料进行混合，搅拌，原料不超过60℃；然后在双螺杆挤出机中挤出，拉丝，水冷，风冷，造粒，得到阻燃高导热护套材料。
6.根据权利要求5所述的一种阻燃高导热护套材料的制备方法，其特征在于：所述搅拌速率为500-800rpm，搅拌时间为3-8min；挤出温度为180℃。
7.一种如权利要求1-4任一所述的阻燃高导热护套材料的应用，其特征在于：用于交联阻燃电缆护套材料的制备，包括：阻燃高导热护套材料和电缆材料共混挤出后进行辐照交联，即得交联阻燃电缆护套材料。
8.根据权利要求7所述的一种阻燃高导热护套材料的应用，其特征在于：所述辐照交联为：高能电子加速器下常温进行辐照交联，辐照剂量为50-80kGy。
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CN102408620A (zh) * 2011-09-26 2012-04-11 泛亚电缆集团有限公司 一种环保型电缆护套料及其制备方法
CN102850645A (zh) * 2012-10-12 2013-01-02 无锡市明珠电缆有限公司 一种辐照交联阻燃电缆护套材料及其制备方法
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CN102408620A (zh) * 2011-09-26 2012-04-11 泛亚电缆集团有限公司 一种环保型电缆护套料及其制备方法
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