CN107474372B - Ul电子线用150℃辐照交联低烟无卤阻燃聚烯烃电缆料及其制备方法 - Google Patents

Ul电子线用150℃辐照交联低烟无卤阻燃聚烯烃电缆料及其制备方法 Download PDF

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CN107474372B
CN107474372B CN201710531554.8A CN201710531554A CN107474372B CN 107474372 B CN107474372 B CN 107474372B CN 201710531554 A CN201710531554 A CN 201710531554A CN 107474372 B CN107474372 B CN 107474372B
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高晓慧
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Abstract

本发明公开一种UL电子线用150℃辐照交联低烟无卤阻燃聚烯烃电缆料,由以下组分制备而成:线性低密度聚乙烯、乙烯‑醋酸乙烯酯共聚物、乙烯‑辛烯共聚物、聚二甲基‑甲基乙烯基‑甲基β‑氰乙基聚硅氧烷橡胶、马来酸酐接枝三元乙丙共聚物、氢氧化铝、乙烯基‑三(2‑甲氧基乙氧基)硅烷、硅油、三烯丙基异氰脲酸酯、改性纳米二氧化钛、4,4'‑硫代双(6‑叔丁基‑3‑甲基苯酚)、硫代二丙酸二硬脂醇酯。本发明具有优异的耐热氧老化性能、较高的力学性能、低烟无卤阻燃、加工性能优异等特点,用其制成的电缆使用寿命长,尤其适用于耐高温电子线等产品。

Description

UL电子线用150℃辐照交联低烟无卤阻燃聚烯烃电缆料及其 制备方法
技术领域
本发明涉及无卤阻燃电缆料技术领域,尤其涉及一种UL电子线用150℃辐照交联低烟无卤阻燃聚烯烃电缆料。
背景技术
电子线作为电子信息产品的重要组成部件,被誉为电子电气类产品的“血管”和“神经”。得益于电子信息产业的迅猛发展,我国电子线行业也以年均45~50%的速度增长,并逐渐朝着“细、薄、安全、环保、高速传输”的方向发展。这就要求材料具有加工性能优异、较高的力学性能、低烟无卤阻燃、优异的耐热氧老化性能。
目前在国内已公开的专利文献中,150℃辐照交联低烟无卤阻燃聚烯烃电缆料产品已有多种,如专利CN201110212510.1公开了一种汽车线用150℃辐照交联低烟无卤阻燃聚烯烃料及其制备;CN201110212519.2公开了一种150℃机车线用辐照交联低烟无卤阻燃聚烯烃料及其制备; CN201210563509.8公开了一种150℃辐照交联低烟无卤阻燃电缆料;CN201310751428.5公开了一种耐温等级为150℃的辐照交联低烟无卤电缆料配方及其制备方法,上述产品多应用于汽车线、机车线等,其性能指标对比详见下表。
表1
Figure 633846DEST_PATH_IMAGE002
由于应用在耐高温电子线的相关产品,不仅要求高强度,而且其耐老化要求使用UL换气烘箱,性能要求极高,上述公开专利中的产品都无法满足其要求,国内市场上也尚未工业化生产,主要采用进口原料,存在成本高等问题。因此,如何克服上述技术问题,成为本领域普通技术人员努力的方向。
发明内容
本发明的目的是提出了一种UL电子线用150℃辐照交联低烟无卤阻燃聚烯烃电缆料,该150℃辐照交联低烟无卤阻燃聚烯烃电缆料具有优异的耐热氧老化性能、较高的力学性能、加工性能优异等特点,用其制成的电缆使用寿命长。
为达到上述目的,本发明采用的技术方案是:一种UL电子线用150℃辐照交联低烟无卤阻燃聚烯烃电缆料,其特征在于,由以下重量份的原料制备而成:
线性低密度聚乙烯 25~40份,
乙烯-醋酸乙烯酯共聚物 40~55份,
乙烯-辛烯共聚物 20~30份,
聚二甲基-甲基乙烯基-甲基β-氰乙基聚硅氧烷橡胶 5~10份,
马来酸酐接枝三元乙丙共聚物 5~15份,
氢氧化铝 90~130份,
乙烯基-三(2-甲氧基乙氧基)硅烷 1~1.2份,
三烯丙基异氰脲酸酯 1.5~3份,
4,4'-硫代双(6-叔丁基-3-甲基苯酚) 2~3份,
硫代二丙酸二硬脂醇酯 1~2份,
硅油 1~2份,
改性纳米二氧化钛 4~6份;
其中,所述的线性低密度聚乙烯、乙烯-醋酸乙烯共聚物、乙烯-辛烯共聚物、聚二甲基-甲基乙烯基-甲基β-氰乙基聚硅氧烷橡胶和马来酸酐接枝三元乙丙共聚物的总重量份数为100份;
线性低密度聚乙烯的熔体指数为2~5g/10min;
乙烯-醋酸乙烯酯共聚物的醋酸乙烯酯百分含量为质量分数28~50%;
改性纳米二氧化钛为通过(3-巯丙基)三甲氧基硅烷改性的表面接枝2-[1-(2-羟基-3,5-二特戊基苯基)乙撑]-4,6-二特戊基苯基丙烯酸酯的金红石型纳米二氧化钛;
所述改性纳米二氧化钛的化学结构式为:
Figure 2
所述改性纳米二氧化钛、4,4'-硫代双(6-叔丁基-3-甲基苯酚) 和硫代二丙酸二硬脂醇酯的重量份数比为(3~5):2:1。
上述技术方案进一步改进的技术方案如下:
1. 上述方案中,所述的改性纳米二氧化钛中2-[1-(2-羟基-3,5-二特戊基苯基)乙撑]-4,6-二特戊基苯基丙烯酸酯的接枝量占改性纳米二氧化钛重量的10~12%。
2. 上述方案中,所述聚二甲基-甲基乙烯基-甲基β-氰乙基聚硅氧烷橡胶乙烯基含量0.13%~0.22%,β-氰乙基含量20%~25%。(也是发明点)
3. 上述方案中,所述马来酸酐接枝三元乙丙共聚物的接枝率为0.8~1.2%。
4. 上述方案中,所述的改性纳米二氧化钛、4,4'-硫代双(6-叔丁基-3-甲基苯酚)和硫代二丙酸二硬脂醇酯的重量份数比为4:2:1。
本发明还提供了一种上述UL电子线用150℃辐照交联低烟无卤阻燃聚烯烃电缆料的制备方法:
步骤一、将按配方重量计量的乙烯-醋酸乙烯酯共聚物、氢氧化铝、乙烯基-三(2-甲氧基乙氧基)硅烷、聚二甲基-甲基乙烯基-甲基β-氰乙基聚硅氧烷橡胶,充分混合后,放入80~90℃的密炼机中混炼,经温度为60~90℃的单螺杆挤出造粒;
步骤二、将上述粒子和按配方重量计量的线性低密度聚乙烯、乙烯-辛烯共聚物、马来酸酐接枝三元乙丙共聚物、三烯丙基异氰脲酸酯、改性纳米二氧化钛、4,4'-硫代双(6-叔丁基-3-甲基苯酚)、硫代二丙酸二硬脂醇酯、硅油,放入高速混合机中混合30秒钟,经温度为130~160℃的双螺杆挤出造粒。
由于上述技术方案的运用,本发明与现有技术相比具有下列优点:
1、本发明150℃辐照交联低烟无卤阻燃聚烯烃电缆料,采用的改性纳米二氧化钛,其表面接枝的2-[1-(2-羟基-3,5-二特戊基苯基)乙撑]-4,6-二特戊基苯基丙烯酸酯的熔点低、不易于在本基材体系中结晶,不会因喷爽、迁移而损失,所以在本基材体系中具有较高的抗氧化活性,和4,4'-硫代双(6-叔丁基-3-甲基苯酚)搭配使用,并在硫代二丙酸二硬脂醇酯的协同作用下,耐热氧老化效果极好,经UL换气烘箱180℃7天老化后,拉伸性能保留率达80%以上。(对应对比例1)
2、本发明150℃辐照交联低烟无卤阻燃聚烯烃电缆料,其改性纳米二氧化钛,采用的是金红石型,不但可作为白色颜料使用,而且其耐候性、耐热性较好;改性后由于其表面接枝的2-[1-(2-羟基-3,5-二特戊基苯基)乙撑]-4,6-二特戊基苯基丙烯酸酯分子中含有庞大的叔戊基,降低了其极性,使其与线性低密度聚乙烯、乙烯-辛烯共聚物、乙烯-醋酸乙烯酯共聚物、聚二甲基-甲基乙烯基-甲基β-氰乙基聚硅氧烷橡胶的相容性得到了提高,既而获得了较好的拉伸性能。(对应对比例2)
3、本发明150℃辐照交联低烟无卤阻燃聚烯烃电缆料,其采用聚二甲基-甲基乙烯基-甲基β-氰乙基聚硅氧烷橡胶与线性低密度聚乙烯、乙烯-辛烯共聚物、乙烯-醋酸乙烯酯共聚物按照合理配比进行搭配,改善了材料的拉伸性能和加工性能,制成线缆可以通过FT2水平燃烧试验,烟密度低、透光率好,可用于耐高温电子线等产品。(对应对比例3)。
具体实施方式
下面结合实施例对本发明作进一步描述:
实施例1~3和对比例1~3:一种UL电子线用150℃辐照交联低烟无卤阻燃聚烯烃电缆料,由表2所示的以下重量份的组分组成:
表2
Figure 517675DEST_PATH_IMAGE004
从实施例和对比例1比较说明:改性纳米二氧化钛、4,4'-硫代双(6-叔丁基-3-甲基苯酚) 和硫代二丙酸二硬脂醇酯的重量份数比应为为(3~5):2:1。
其中,线性低密度聚乙烯的熔体指数为2g/10min;乙烯-醋酸乙烯酯共聚物的醋酸乙烯酯百分含量为质量分数33%;改性纳米二氧化钛化学结构式为:
Figure 1
其表面2-[1-(2-羟基-3,5-二特戊基苯基)乙撑]-4,6-二特戊基苯基丙烯酸酯的接枝量占改性纳米二氧化钛重量的10%;马来酸酐接枝三元乙丙共聚物的接枝率为1.2%;聚二甲基-甲基乙烯基-甲基β-氰乙基聚硅氧烷橡胶中乙烯基含量0.13%~0.22%,β-氰乙基含量20%~25%。
一种用于上述实施例1~3和对比例1~3的UL电子线用150℃辐照交联低烟无卤阻燃聚烯烃电缆料的制备方法,包括以下步骤:
步骤一、将按配方重量计量的乙烯-醋酸乙烯酯共聚物、氢氧化铝、乙烯基-三(2-甲氧基乙氧基)硅烷、聚二甲基-甲基乙烯基-甲基β-氰乙基聚硅氧烷橡胶,充分混合后,放入80~90℃的密炼机中混炼,经温度为60~90℃的单螺杆挤出造粒;
步骤二、将上述粒子和按配方重量计量的线性低密度聚乙烯、乙烯-辛烯共聚物、马来酸酐接枝三元乙丙共聚物、三烯丙基异氰脲酸酯、改性纳米二氧化钛(或纳米二氧化钛和2-[1-(2-羟基-3,5-二特戊基苯基)乙撑]-4,6-二特戊基苯基丙烯酸酯)、4,4'-硫代双(6-叔丁基-3-甲基苯酚)、硫代二丙酸二硬脂醇酯、硅油,放入高速混合机中混合30秒钟,经温度为130~160℃的双螺杆挤出造粒。
实施例1~3和对比例1~3所制得的UL电子线用150℃辐照交联低烟无卤阻燃聚烯烃电缆料经压片、辐照剂量为12Mrad的处理后性能测试数据如表2所示:
表2
Figure 934715DEST_PATH_IMAGE006
从表2的性能测试结果可以看出,本发明的UL电子线用150℃辐照交联低烟无卤阻燃聚烯烃电缆料,具有优异的耐热氧老化性能、较高的力学性能、低烟无卤阻燃、加工性能优异等特点,用其制成的电缆使用寿命长,且成本低。
上述实施例只为说明本发明的技术构思及特点,其目的在于让熟悉此项技术的人士能够了解本发明的内容并据以实施,并不能以此限制本发明的保护范围。凡根据本发明精神实质所作的等效变化或修饰,都应涵盖在本发明的保护范围之内。

Claims (6)

1.一种UL电子线用150℃辐照交联低烟无卤阻燃聚烯烃电缆料,其特征在于,由以下重量份的原料制备而成:
线性低密度聚乙烯 25~40份,
乙烯-醋酸乙烯酯共聚物 40~55份,
乙烯-辛烯共聚物 20~30份,
聚二甲基-甲基乙烯基-甲基β-氰乙基聚硅氧烷橡胶 5~10份,
马来酸酐接枝三元乙丙共聚物 5~15份,
氢氧化铝 90~130份,
乙烯基-三(2-甲氧基乙氧基)硅烷 1~1.2份,
三烯丙基异氰脲酸酯 1.5~3份,
4,4'-硫代双(6-叔丁基-3-甲基苯酚) 2~3份,
硫代二丙酸二硬脂醇酯 1~2份,
硅油 1~2份,
改性纳米二氧化钛 4~6份;
其中,所述的线性低密度聚乙烯、乙烯-醋酸乙烯共聚物、乙烯-辛烯共聚物、聚二甲基-甲基乙烯基-甲基β-氰乙基聚硅氧烷橡胶和马来酸酐接枝三元乙丙共聚物的总重量份数为100份;
线性低密度聚乙烯的熔体指数为2~5g/10min;
乙烯-醋酸乙烯酯共聚物的醋酸乙烯酯百分含量为质量分数28~50%;
改性纳米二氧化钛为通过(3-巯丙基)三甲氧基硅烷改性的表面接枝2-[1-(2-羟基-3,5-二特戊基苯基)乙撑]-4,6-二特戊基苯基丙烯酸酯的金红石型纳米二氧化钛;
所述改性纳米二氧化钛的化学结构式为:
Figure 237499DEST_PATH_IMAGE001
所述改性纳米二氧化钛、4,4'-硫代双(6-叔丁基-3-甲基苯酚) 和硫代二丙酸二硬脂醇酯的重量份数比为(3~5):2:1。
2.根据权利要求1所述的UL电子线用150℃辐照交联低烟无卤阻燃聚烯烃电缆料,所述改性纳米二氧化钛中2-[1-(2-羟基-3,5-二特戊基苯基)乙撑]-4,6-二特戊基苯基丙烯酸酯的接枝量占改性纳米二氧化钛重量的10~12%。
3.根据权利要求1所述的UL电子线用150℃辐照交联低烟无卤阻燃聚烯烃电缆料, 所述聚二甲基-甲基乙烯基-甲基β-氰乙基聚硅氧烷橡胶乙烯基含量0.13%~0.22%,β-氰乙基含量20%~25%。
4.根据权利要求1所述的UL电子线用150℃辐照交联低烟无卤阻燃聚烯烃电缆料,所述马来酸酐接枝三元乙丙共聚物的接枝率为0.8~1.2%。
5.根据权利要求1所述的UL电子线用150℃辐照交联低烟无卤阻燃聚烯烃电缆料,所述改性纳米二氧化钛、4,4'-硫代双(6-叔丁基-3-甲基苯酚) 和硫代二丙酸二硬脂醇酯的重量份数比为4:2:1。
6.一种用于权利要求1~5任一项所述UL电子线用150℃辐照交联低烟无卤阻燃聚烯烃电缆料的制备方法,其特征在于,包括以下两步:
步骤一、将按配方重量计量的乙烯-醋酸乙烯酯共聚物、氢氧化铝、乙烯基-三(2-甲氧基乙氧基)硅烷、聚二甲基-甲基乙烯基-甲基β-氰乙基聚硅氧烷橡胶,充分混合后,放入80~90℃的密炼机中混炼,经温度为60~90℃的单螺杆挤出造粒;
步骤二、将上述粒子和按配方重量计量的线性低密度聚乙烯、乙烯-辛烯共聚物、马来酸酐接枝三元乙丙共聚物、三烯丙基异氰脲酸酯、改性纳米二氧化钛、4,4'-硫代双(6-叔丁基-3-甲基苯酚)、硫代二丙酸二硬脂醇酯、硅油,放入高速混合机中混合30秒钟,经温度为130~160℃的双螺杆挤出造粒。
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