CN116589777A - 一种无卤阻燃交联聚乙烯电缆料及其制备方法 - Google Patents
一种无卤阻燃交联聚乙烯电缆料及其制备方法 Download PDFInfo
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Abstract
本发明涉及改性电缆料的技术领域,提供了一种无卤阻燃交联聚乙烯电缆料及其制备方法。先以3‑氨丙基三甲氧基硅烷对膨胀石墨粉进行表面改性,得到氨基化膨胀石墨粉;然后以螺环磷酰二氯与二烯丙基胺以摩尔比1.05‑1.1:1反应,得到产物A;再以产物A与氨基化膨胀石墨粉进行固相反应,得到产物B;最后以预辐照聚乙烯、产物B、抗氧剂混合进行反应性挤出造粒,制得以产物B为交联点的聚乙烯电缆料。本发明制备的聚乙烯电缆料不仅具有良好的阻燃性能,而且具有良好的抗拉性能。
Description
技术领域
本发明涉及改性电缆料的技术领域,提供了一种无卤阻燃交联聚乙烯电缆料及其制备方法。
背景技术
在电力发展过程中,电缆作为运送电力的基本工具,有着举足轻重的作用。在电缆制备方面,聚合物材料常被用作制备绝缘层或护套,比如聚氯乙烯、氯丁橡胶、聚乙烯等,其中,聚乙烯具有优良的力学性能、电性能和耐化学腐蚀性能,且价格低廉,成为用量较大的电缆料之一。
作为电缆制备原料的聚乙烯材料,具有氧指数低、易燃、燃烧热高等缺点,在电气火灾中容易成为可燃物,有着极大的安全隐患,因此,需要加入阻燃剂对其进行改性。然而,过多的阻燃剂在提高阻燃性的同时,可能会影响材料的力学性能,比如降低抗拉强度,尤其是当阻燃剂与聚乙烯的界面相容性较差时更为明显。
常用于聚合物的阻燃剂中,膨胀型阻燃剂以其阻燃效率高、自熄性好、低烟、低毒、无腐蚀性气体等优势而备受重视。膨胀型阻燃剂分为化学膨胀型阻燃剂(氮磷系膨胀阻燃剂)和物理膨胀型阻燃剂(膨胀石墨)。化学膨胀型阻燃剂通过酸源、气源、炭源的综合作用,受热时酸源和炭源发生酯化反应,大量酯化物脱水后形成炭层,并在气源作用下形成泡沫炭层。而膨胀石墨是通过受热时其本身体积膨胀形成致密炭层来实现阻燃的。
申请号为202110058463.3的中国发明专利公开了一种无卤阻燃防火电缆及其制备方法。无卤阻燃防火电缆包括如下重量份数的组分:高密度聚乙烯40-60份;线性低密度聚乙烯30-40份;乙烯-醋酸乙烯共聚物200-300份;相容剂30-40份;抗氧剂5-10份;润滑剂5-10份;增塑剂10-20份;可膨胀石墨20-40份;聚磷酸铵40-80份;改性纳米氢氧化镁10-20份。其制备方法为:将各原料混合,加入添加剂搅拌,挤出造粒,得到电缆料,将电缆料熔融挤出,包覆在线材表面,冷却固化。
申请号为201710287750.5的中国发明专利公开了一种环保交联聚乙烯控制电缆,包括控制电缆线芯和绝缘层,所述绝缘层由以下质量份数的组分制成:聚乙烯45-60份,氢氧化镁25-35份,可膨胀石墨25-30份,润滑剂0.1-0.4份,改性剂0.2-0.5份,硅烷交联剂0.3-0.9份。该控制电缆的绝缘层阻燃剂不含卤素,遇火后不仅能够阻燃还能避免产生大量烟雾和有毒卤化氢气体,安全环保。
发明内容
本发明提供了一种无卤阻燃交联聚乙烯电缆料及其制备方法,目的在于获得阻燃性能和抗拉性能均较好的聚乙烯环保电缆料。
本发明提供了一种无卤阻燃交联聚乙烯电缆料的制备方法,所述电缆料制备的具体步骤如下:
(1)将膨胀石墨粉加入乙醇/水中,超声分散均匀,高速搅拌,加入3-氨丙基三甲氧基硅烷,在40℃反应2-3h,抽滤,依次用乙醇和去离子水洗涤,真空干燥,得到氨基化膨胀石墨粉;膨胀石墨粉、3-氨丙基三甲氧基硅烷、乙醇、水的质量比为1-1.2:4-6:50:50;
(2)将二烯丙基胺溶于二氯甲烷/二氧六环混合溶剂中,加入螺环磷酰二氯搅拌混合,再滴加三乙胺,加热至42℃回流反应5-7h,抽滤,依次用二甲基甲酰胺和丙酮洗涤,真空干燥,得到产物A;二烯丙基胺、螺环磷酰二氯、三乙胺的摩尔比为1:1.05-1.1:1;
(3)将产物A用粉碎机粉碎,然后与氨基化膨胀石墨粉混合,平铺于锥形反应器底部,置于230-250℃油浴中,搅拌反应4-6h,然后用丙酮洗涤,真空干燥,得到产物B;产物A、氨基化膨胀石墨粉的质量比为2-3:10;
(4)采用β射线对聚乙烯进行预辐照,然后与产物B、抗氧剂混合,加入反应型双螺杆挤出机中,经挤出造粒,得到无卤阻燃交联聚乙烯电缆料;聚乙烯、产物B、抗氧剂的质量比为100:20-30:0.2-0.5。
公知的,螺环磷酰二氯具有两个可反应基团(-PO3Cl),可与氨基(-NH2或-NH-)反应,生成的产物是一种化学膨胀型阻燃剂(含有酸源、气源、炭源)。膨胀石墨粉是一种物理膨胀型阻燃剂,因表面含有羧基、羟基而具有反应活性。二烯丙基胺的结构中含有两个C=C和一个-NH-,既具有与螺环磷酰二氯反应的能力(通过-NH-),又具有与聚烯烃接枝的能力(通过C=C)。
首先,采用3-氨丙基三甲氧基硅烷与膨胀石墨粉表面的活性基团反应,得到氨基化膨胀石墨粉。为防止硅烷水解发生自聚合,应在高速搅拌下加入3-氨丙基三甲氧基硅烷。优选的,步骤(1)中,高速搅拌的转速为200-400rpm。
然后,以三乙胺为缚酸剂,使螺环磷酰二氯的一个可反应基团与二烯丙基胺的-NH-反应,得到产物A。产物A的结构中还有一个可反应基团,以及两个C=C。为防止一个螺环磷酰二氯分子中的两个可反应基团均与-NH-发生反应,应使螺环磷酰二氯的摩尔数过量,以过量5-10%为宜,即二烯丙基胺、螺环磷酰二氯的摩尔比为1:1.05-1.1。优选的,步骤(2)中,二烯丙基胺、二氯甲烷、二氧六环的质量比为2-4:50:50。
接着,将产物A与氨基化膨胀石墨粉混合进行固相反应,反应过程中持续搅拌使二者充分接触,产物A的可反应基团与膨胀石墨粉表面的氨基反应,将产物A接枝在膨胀石墨粉表面,形成核壳结构的产物B。可见,产物B的核层为物理膨胀阻燃组分,壳层为化学膨胀阻燃组分,并且壳层上含有许多C=C。
最后,先对聚乙烯进行预辐照处理,再与产物B、抗氧剂混合进行反应性挤出造粒,产物B通过壳层上的C=C接枝到聚乙烯大分子链上,形成以产物B为交联点的聚乙烯粒料,即无卤阻燃交联聚乙烯电缆料。优选的,步骤(4)中,预辐照的辐照剂量为15-20kGy;聚乙烯为HDPE、LDPE、LLDPE中的一种或几种;抗氧剂包括抗氧剂1010、抗氧剂1098、抗氧剂1076、抗氧剂1024中的一种或几种。
本发明还提供了以上制备方法制备得到的无卤阻燃交联聚乙烯电缆料,具有以下有益效果:
第一,本发明采用螺环磷酰二氯与二烯丙基胺反应制备产物A,再将产物A接枝在膨胀石墨粉表面得到产物B。在材料燃烧时,产物B同时具有化学膨胀型阻燃剂和物理膨胀型阻燃剂的双重作用,可明显提高聚乙烯电缆料的阻燃性能。
第二,产物B的壳层上含有许多C=C,通过C=C与预辐照聚乙烯反应,形成以产物B为交联点的交联聚乙烯。产物B的核层是石墨粒子,石墨粒子位于聚乙烯网络结构的交联点位置,与直接将石墨粒子分散在交联聚乙烯中相比,本发明中的石墨粒子可发挥更好的增强作用,所得电缆料具有更高的抗拉强度。
第三,由于产物B的核层与壳层之间、壳层与聚乙烯之间均具有化学键连接,产物B可在电缆料中分布均匀,在材料未燃烧时有利于石墨粒子发挥增强作用,在材料燃烧时可实现均匀膨胀,促进形成均匀致密的炭层,有利于提高阻燃性能。
第四,本发明以螺环磷酰二氯为原料,最终其结构中的两个可反应基团均与氨基反应,即两个氯原子均被反应除去,因而产物B中不含卤素,所得电缆料为无卤环保电缆料。
具体实施方式
以下通过具体实施方式对本发明作进一步的详细说明,但不应将此理解为本发明的范围仅限于以下的实例。在不脱离本发明上述方法思想的情况下,根据本领域普通技术知识和惯用手段做出的各种替换或变更,均应包含在本发明的范围内。以下实施例和对比例中,聚乙烯为LLDPE,抗氧剂为抗氧剂1010,膨胀石墨粉的起始膨胀温度为300℃。
实施例1
(1)将膨胀石墨粉加入乙醇/水中,超声分散均匀,以300rpm高速搅拌,加入3-氨丙基三甲氧基硅烷,在40℃反应2.5h,抽滤,依次用乙醇和去离子水洗涤,真空干燥,得到氨基化膨胀石墨粉;膨胀石墨粉、3-氨丙基三甲氧基硅烷、乙醇、水的质量比为1.2:5:50:50;
(2)将二烯丙基胺溶于二氯甲烷/二氧六环混合溶剂中,加入螺环磷酰二氯搅拌混合,再滴加三乙胺,加热至42℃回流反应7h,抽滤,依次用二甲基甲酰胺和丙酮洗涤,真空干燥,得到产物A;二烯丙基胺、螺环磷酰二氯、三乙胺的摩尔比为1:1.05:1;二烯丙基胺、二氯甲烷、二氧六环的质量比为3:50:50;
(3)将产物A用粉碎机粉碎,然后与氨基化膨胀石墨粉混合,平铺于锥形反应器底部,置于230℃油浴中,搅拌反应6h,然后用丙酮洗涤,真空干燥,得到产物B;产物A、氨基化膨胀石墨粉的质量比为2.5:10;
(4)采用β射线对聚乙烯进行预辐照,然后与产物B、抗氧剂混合,加入反应型双螺杆挤出机中,经挤出造粒,得到阻燃交联聚乙烯电缆料;聚乙烯、产物B、抗氧剂的质量比为100:20:0.3;辐照剂量为20kGy;反应型双螺杆挤出机的反应段温度为185-190℃,螺杆转速为120rpm。
实施例2
(1)将膨胀石墨粉加入乙醇/水中,超声分散均匀,以200rpm高速搅拌,加入3-氨丙基三甲氧基硅烷,在40℃反应3h,抽滤,依次用乙醇和去离子水洗涤,真空干燥,得到氨基化膨胀石墨粉;膨胀石墨粉、3-氨丙基三甲氧基硅烷、乙醇、水的质量比为1.2:5:50:50;
(2)将二烯丙基胺溶于二氯甲烷/二氧六环混合溶剂中,加入螺环磷酰二氯搅拌混合,再滴加三乙胺,加热至42℃回流反应5h,抽滤,依次用二甲基甲酰胺和丙酮洗涤,真空干燥,得到产物A;二烯丙基胺、螺环磷酰二氯、三乙胺的摩尔比为1:1.05:1;二烯丙基胺、二氯甲烷、二氧六环的质量比为3:50:50;
(3)将产物A用粉碎机粉碎,然后与氨基化膨胀石墨粉混合,平铺于锥形反应器底部,置于250℃油浴中,搅拌反应4h,然后用丙酮洗涤,真空干燥,得到产物B;产物A、氨基化膨胀石墨粉的质量比为2.5:10;
(4)采用β射线对聚乙烯进行预辐照,然后与产物B、抗氧剂混合,加入反应型双螺杆挤出机中,经挤出造粒,得到阻燃交联聚乙烯电缆料;聚乙烯、产物B、抗氧剂的质量比为100:25:0.3;辐照剂量为20kGy;反应型双螺杆挤出机的反应段温度为185-190℃,螺杆转速为120rpm。
实施例3
(1)将膨胀石墨粉加入乙醇/水中,超声分散均匀,以400rpm高速搅拌,加入3-氨丙基三甲氧基硅烷,在40℃反应2h,抽滤,依次用乙醇和去离子水洗涤,真空干燥,得到氨基化膨胀石墨粉;膨胀石墨粉、3-氨丙基三甲氧基硅烷、乙醇、水的质量比为1.2:5:50:50;
(2)将二烯丙基胺溶于二氯甲烷/二氧六环混合溶剂中,加入螺环磷酰二氯搅拌混合,再滴加三乙胺,加热至42℃回流反应6h,抽滤,依次用二甲基甲酰胺和丙酮洗涤,真空干燥,得到产物A;二烯丙基胺、螺环磷酰二氯、三乙胺的摩尔比为1:1.1:1;二烯丙基胺、二氯甲烷、二氧六环的质量比为3:50:50;
(3)将产物A用粉碎机粉碎,然后与氨基化膨胀石墨粉混合,平铺于锥形反应器底部,置于240℃油浴中,搅拌反应5h,然后用丙酮洗涤,真空干燥,得到产物B;产物A、氨基化膨胀石墨粉的质量比为2.5:10;
(4)采用β射线对聚乙烯进行预辐照,然后与产物B、抗氧剂混合,加入反应型双螺杆挤出机中,经挤出造粒,得到阻燃交联聚乙烯电缆料;聚乙烯、产物B、抗氧剂的质量比为100:30:0.3;辐照剂量为20kGy;反应型双螺杆挤出机的反应段温度为185-190℃,螺杆转速为120rpm。
对比例1
未对膨胀石墨粉进行氨基化改性,未制备产物B,而是以产物A作为聚乙烯的交联点,膨胀石墨粉直接分散在体系中,具体为:
(1)将二烯丙基胺溶于二氯甲烷/二氧六环混合溶剂中,加入螺环磷酰二氯搅拌混合,再滴加三乙胺,加热至42℃回流反应7h,抽滤,依次用二甲基甲酰胺和丙酮洗涤,真空干燥,得到产物A;二烯丙基胺、螺环磷酰二氯、三乙胺的摩尔比为1:1.05:1;二烯丙基胺、二氯甲烷、二氧六环的质量比为3:50:50;
(2)采用β射线对聚乙烯进行预辐照,然后与产物A、膨胀石墨粉、抗氧剂混合,加入反应型双螺杆挤出机中,经挤出造粒,得到阻燃交联聚乙烯电缆料;聚乙烯、膨胀石墨粉、产物A、抗氧剂的质量比为100:16:4:0.3;辐照剂量为20kGy;反应型双螺杆挤出机的反应段温度为185-190℃,螺杆转速为120rpm。
对比例2
与对比例1的制备方法相同,不同的是:聚乙烯、膨胀石墨粉、产物A、抗氧剂的质量比为100:20:5:0.3。
对比例3
与对比例1的制备方法相同,不同的是:聚乙烯、膨胀石墨粉、产物A、抗氧剂的质量比为100:24:6:0.3。
按照GB/T 2406-2008制成标准样条并测试氧指数;按照UL-94制成标准样条并测试阻燃等级;按照GB/T1040-2006制成标准样条并测试抗拉强度;所得数据如表1所示。
表1:
Claims (7)
1.一种无卤阻燃交联聚乙烯电缆料的制备方法,其特征在于,所述电缆料制备的具体步骤如下:
(1)将膨胀石墨粉加入乙醇/水中,超声分散均匀,高速搅拌,加入3-氨丙基三甲氧基硅烷,在40℃反应2-3h,抽滤,依次用乙醇和去离子水洗涤,真空干燥,得到氨基化膨胀石墨粉;膨胀石墨粉、3-氨丙基三甲氧基硅烷、乙醇、水的质量比为1-1.2:4-6:50:50;
(2)将二烯丙基胺溶于二氯甲烷/二氧六环混合溶剂中,加入螺环磷酰二氯搅拌混合,再滴加三乙胺,加热至42℃回流反应5-7h,抽滤,依次用二甲基甲酰胺和丙酮洗涤,真空干燥,得到产物A;二烯丙基胺、螺环磷酰二氯、三乙胺的摩尔比为1:1.05-1.1:1;
(3)将产物A用粉碎机粉碎,然后与氨基化膨胀石墨粉混合,平铺于锥形反应器底部,置于230-250℃油浴中,搅拌反应4-6h,然后用丙酮洗涤,真空干燥,得到产物B;产物A、氨基化膨胀石墨粉的质量比为2-3:10;
(4)采用β射线对聚乙烯进行预辐照,然后与产物B、抗氧剂混合,加入反应型双螺杆挤出机中,经挤出造粒,得到无卤阻燃交联聚乙烯电缆料;聚乙烯、产物B、抗氧剂的质量比为100:20-30:0.2-0.5。
2.根据权利要求1所述一种无卤阻燃交联聚乙烯电缆料的制备方法,其特征在于:步骤(1)中,高速搅拌的转速为200-400rpm。
3.根据权利要求1所述一种无卤阻燃交联聚乙烯电缆料的制备方法,其特征在于:步骤(2)中,二烯丙基胺、二氯甲烷、二氧六环的质量比为2-4:50:50。
4.根据权利要求1所述一种无卤阻燃交联聚乙烯电缆料的制备方法,其特征在于:步骤(4)中,预辐照的辐照剂量为15-20kGy。
5.根据权利要求1所述一种无卤阻燃交联聚乙烯电缆料的制备方法,其特征在于:步骤(4)中,聚乙烯为HDPE、LDPE、LLDPE中的一种或几种。
6.根据权利要求1所述一种无卤阻燃交联聚乙烯电缆料的制备方法,其特征在于:步骤(4)中,抗氧剂包括抗氧剂1010、抗氧剂1098、抗氧剂1076、抗氧剂1024中的一种或几种。
7.权利要求1-6任一项所述制备方法制备得到的无卤阻燃交联聚乙烯电缆料。
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