CN112940388A - 一种b2级低烟无卤聚烯烃电缆料及其制备方法 - Google Patents
一种b2级低烟无卤聚烯烃电缆料及其制备方法 Download PDFInfo
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Abstract
本发明公开了一种B2级低烟无卤聚烯烃电缆料及其制备方法,B2级低烟无卤聚烯烃电缆料的原料包括如下组分:乙烯‑丙烯酸丁酯共聚物35~50份、乙烯‑乙酸乙烯酯共聚物25~45份、超低密度聚乙烯10~25份、相容剂5~10份、润滑剂3~8份、抗氧剂0.5~2份、无机填料120~150份、纳米蒙脱土1~5份和炭黑母粒3份,其中,无机填料为氢氧化铝和氢氧化镁的混合物,氢氧化铝的粒径为0.5~1.5μm,氢氧化镁的粒径为1.0~1.8μm;所述份数为重量份数。本发明B2级低烟无卤聚烯烃电缆料达到B2级的阻燃级别,且机械性能优良、使用寿命长,利于电缆的加工以及敷设。
Description
技术领域
本发明涉及一种B2级低烟无卤聚烯烃电缆料及其制备方法,属于电线电缆料领域。
背景技术
目前国内电线电缆阻燃等级的评定主要参考GB/T 19666-2019《阻燃和耐火电线电缆或光缆通则》,根据可燃物燃烧体积不同,阻燃性能从难而易分为A、B、C及D类。然而大量的试验数据表明,该方法并不能准确的评价电缆的阻燃性能,例如仪表控制电缆因电缆外径小、绝缘线芯多,其B类成束燃烧的难度远大于A类成束燃烧。近年来,GB/T 31247-2014《电缆及光缆燃烧性能分级》逐渐被市场认可,该标准通过热释放速率峰值、受火1200s内热释放总量、燃烧增长速率指数、产烟速率及产烟总量等试验数据来评价电缆的阻燃性能,而常规低烟无卤电缆料的热释放速率峰值及受火1200s内热释放总量这两项数据往往都不合格。
发明内容
本发明提供一种B2级低烟无卤聚烯烃电缆料及其制备方法,本发明B2级低烟无卤聚烯烃电缆料,在解决常规低烟无卤电缆料热释放速率峰值和受火1200s内热释放总量不足的同时,机械性能优于国标GB/T32129《电线电缆用无卤低烟阻燃电缆料》中规定的要求;本发明通过选择超细粒径的氢氧化铝和氢氧化镁及确定两者合适的添加比例,大大降低电缆料的热释放速率;通过添加纳米蒙脱土形成致密的蜂窝状炭层来隔氧隔热,从而与氢氧化物阻燃剂起到协同作用;通过添加超低密度聚乙烯,大大提高电缆料的机械性能。
为解决上述技术问题,本发明所采用的技术方案如下:
一种B2级低烟无卤聚烯烃电缆料,其原料包括如下组分:
其中,无机填料为氢氧化铝和氢氧化镁的混合物,氢氧化铝的粒径为0.5~1.5μm,氢氧化镁的粒径为1.0~1.8μm;所述份数为重量份数。
乙烯-丙烯酸丁酯共聚物简称EBA,乙烯-乙酸乙烯酯共聚物简称为EVA,超低密度聚乙烯简称为ULDPE。
申请人经研究发现,在聚烯烃电缆料中加入细粒径氢氧化铝和氢氧化镁可以产生明显的协同效应;氢氧化物的粒径越细、表面积越大,其与聚合物接触面积就越大,在发生火灾时阻燃剂能最大效率的吸收燃烧热量,极大限度的减少聚合物分解,从而降低热释放速率和热释放总量;
优选的,氢氧化铝与氢氧化镁的质量比为6:1~2:1,且当氢氧化铝和氢氧化镁添加比例为4:1时,电缆料的阻燃性能最佳;纳米蒙脱土的加入能形成致密的蜂窝状炭层,较好的隔绝了氧气与燃烧物的接触,起到协效阻燃的作用;乙烯-丙烯酸丁酯共聚物、乙烯-乙酸乙烯酯共聚物和超低密度聚乙烯特定比例的结合,可增强电缆料的机械性能,同时确保物料结合的稳定性,进而确保阻燃和机械性能的长效性;本申请通过对原料组分及用量的选择,使它们之间的协同效应发挥到最佳,从而制得了B2级低烟无卤聚烯烃电缆料。
为了进一步确保B2级低烟无卤聚烯烃电缆料的低温柔软性能,优选,乙烯-丙烯酸丁酯共聚物中丙烯酸丁酯的质量含量为15%~30%,熔融指数为1.5~3g/10min。
为了进一步兼顾B2级低烟无卤聚烯烃电缆料柔软性和稳定性,乙烯-乙酸乙烯酯共聚物中乙酸乙烯酯的质量含量为25%~50%,熔融指数为3~6g/10min。
为了进一步保证B2级低烟无卤聚烯烃电缆料的理化性能,同时促进各组分之间的协同效应,提高阻燃性,优选,超低密度聚乙烯的熔融指数为1.5~3.5g/10min。
为了进一步保证B2级低烟无卤聚烯烃电缆料的均匀性,同时进一步促进各组分之间的协同效应,相容剂为马来酸酐接枝乙烯—辛烯共聚物、马来酸酐接枝乙烯—乙酸乙烯酯共聚物或马来酸酐接枝茂金属线性低密度聚乙烯中的至少一种,进一步优选,相容剂为马来酸酐接枝乙烯—辛烯共聚物和马来酸酐接枝乙烯—乙酸乙烯酯共聚物质量比为(1.5~2.5):1的混合物,更有选为2:1的混合物。
为了提高物料加工性能,同时进一步促进各组分之间的协同效应,润滑剂为乙撑双硬脂酸酰胺、油酰胺、硅酮母粒、硬脂酸锌或聚乙烯蜡中的至少一种;进一步优选,润滑剂为油酸酰胺和硅酮母粒(硅酮含量为60%)质量比为1:(1~3)的混合物,更优选为1:1的混合物。
为了提高B2级低烟无卤聚烯烃电缆料耐候性的同时,促进各组分之间协同效应,优选,抗氧剂为四[β-(3,5-二叔丁基-4-羟基苯基)丙酸]季戊四醇酯和三[2,4-二叔丁基苯基]亚磷酸酯质量比为(1~3):1的混合物。
为了进一步提高B2级低烟无卤聚烯烃电缆料的综合性能,尤其是高阻燃低烟性,优选,纳米蒙脱土表面经钛酸酯处理,平均粒径为1~50nm。
为了确保产品的外观和均匀性,炭黑母粒中,炭黑的质量含量为50%,炭黑的粒径为1.0~3.0μm。
上述B2级低烟无卤聚烯烃电缆料的制备方法,将乙烯-丙烯酸丁酯共聚物、乙烯-乙酸乙烯酯、超低密度聚乙烯、相容剂、润滑剂、抗氧剂、炭黑母粒、无机填料和纳米蒙脱土依次加入捏炼机捏练,然后经双阶机组挤出造粒;其中,实测捏炼机出料温度为155℃~165℃,捏炼时间为15-16min,捏炼过程中上顶栓每3min抬起一次,确保物料混合均匀;双阶机组中双螺杆和单螺杆温度设定范围均为110℃~125℃。
本发明未提及的技术均参照现有技术。
本发明B2级低烟无卤聚烯烃电缆料,低烟无卤、且阻燃性能优异,可满足GB/T31247-2014《电缆及光缆燃烧性能分级》中B2级燃烧性能要求,且机械性能优良、使用寿命长,利于电缆的加工以及敷设。
具体实施方式
为了更好地理解本发明,下面结合实施例进一步阐明本发明的内容,但本发明的内容不仅仅局限于下面的实施例。
实施例1~5B2级低烟无卤聚烯烃电缆料原料组分如表1所示。
表1实施例1~5B2级低烟无卤聚烯烃电缆料原料组分
表1中EBA为雷普索尔的EBA 2770;EVA为阿科玛的2803;超低密度聚乙烯为三井杜邦的SP0540和SP1071C;相容剂为上海久聚的9967和JCP1000的2:1混合物;硅酮母粒为上海武江PMAF-15;抗氧剂为天津力生1010和天津利安隆168的1:1混合物;炭黑母粒为卡博特的2762;表中单位为重量份数。
氢氧化铝和氢氧化镁表面已经过硬脂酸处理,由艾特克阻燃材料有限公司提供;纳米蒙脱土已经过钛酸酯处理,由浙江丰虹新材料股份有限公司提供。
各实施例中B2级低烟无卤聚烯烃电缆料的制备方法为:按表1的配比准确称量,将乙烯—丙烯酸丁酯共聚物、乙烯-乙酸乙烯酯共聚物、超低密度聚乙烯、相容剂、润滑剂、抗氧剂、炭黑母粒、无机填料和纳米蒙脱土依次加入捏炼机捏炼,然后经双阶机组挤出造粒;其中,实测捏炼机出料温度控制为155℃~165℃,捏炼时间为15min,捏炼过程中上顶栓每3min抬起一次,确保物料混合均匀,双螺杆及单螺杆温度控制范围为110℃~125℃。
检测:将各实施例所得粒料在平板硫化机上经175℃*10min压片,压力为15Mpa,样片厚度1mm,在室温下放置16h后测试常规性能,具体见表2。其中,机械性能测试方法参考标准为GB/T 1040。将电缆料做为外护套,制备成品电缆并开展B2级燃烧试验,试验标准为GB/T31248《电缆或光缆在受火条件下火焰蔓延、热释放和产烟特性的试验方法》,燃烧性能评级参考GB/T31247《电缆及光缆燃烧性能分级》。
表2
对比实施例1和实施例2可以看出,当氢氧化铝和氢氧化镁比例为4:1时,电缆料的阻燃性能会有明显提升,这可能是因为氢氧化铝的分解温度为220℃,而氢氧化镁分解温度为340℃(与聚烯烃热分解温度相同),两者按一定比例添加会起到协同分段阻燃的作用;对比实施例2和实施例3可以看出,不添加纳米蒙脱土时,电缆不能通过B2级燃烧试验,这是因为添加少量的蒙脱土后,电缆料在燃烧过程中能形成均匀致密的蜂窝状炭层,可以起到隔热隔氧的作用,从而降低电缆料的热释放速率;对比实施例2和实施例4可以看出,随着超低密度聚乙烯添加量的增加,电缆料的机械性能有明显提高,这是因为超低密度聚乙烯兼具强度和柔软的分子链,受外界拉力时,柔软的分子链对无机填料起到“保护”作用,大大的降低了因无机填料成为应力集中点而使材料断裂的可能,因此拉伸强度和断裂伸长率有明显增加;对比实施例2和实施例5可以看出,氢氧化铝和氢氧化镁粒径对阻燃性能也有影响,这是因为氢氧化铝和氢氧化镁的粒径越细,其比表面积越大,与聚烯烃树脂接触面积就越大,在受火燃烧时,其阻燃效率就越高,从而最大限度的降低聚烯烃分解。
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目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 (10)
2.根据权利要求1所述的B2级低烟无卤聚烯烃电缆料,其特征在于:乙烯-丙烯酸丁酯共聚物中丙烯酸丁酯的质量含量为15%~30%,熔融指数为1.5~3g/10min。
3.根据权利要求1或2所述的B2级低烟无卤聚烯烃电缆料,其特征在于:乙烯-乙酸乙烯酯共聚物中乙酸乙烯酯的质量含量为25%~50%,熔融指数为3~6g/10min。
4.根据权利要求1或2所述的B2级低烟无卤聚烯烃电缆料,其特征在于:超低密度聚乙烯熔融指数为1.5~3.5g/10min。
5.根据权利要求1或2所述的B2级低烟无卤聚烯烃电缆料,其特征在于:相容剂为马来酸酐接枝乙烯—辛烯共聚物、马来酸酐接枝乙烯—乙酸乙烯酯共聚物或马来酸酐接枝茂金属线性低密度聚乙烯中的至少一种;润滑剂为乙撑双硬脂酸酰胺、油酰胺、硅酮母粒、硬脂酸锌或聚乙烯蜡中的至少一种。
6.根据权利要求5所述的B2级低烟无卤聚烯烃电缆料,其特征在于:相容剂为马来酸酐接枝乙烯—辛烯共聚物和马来酸酐接枝乙烯—乙酸乙烯酯共聚物质量比为(1.5~2.5):1的混合物;润滑剂为油酸酰胺和硅酮母粒(硅酮含量为60%)质量比为1:(1~3)的混合物。
7.根据权利要求1或2所述的B2级低烟无卤聚烯烃电缆料,其特征在于:抗氧剂为四[β-(3,5-二叔丁基-4-羟基苯基)丙酸]季戊四醇酯和三[2,4-二叔丁基苯基]亚磷酸酯质量比为(1~3):1的混合物。
8.根据权利要求1或2所述的B2级低烟无卤聚烯烃电缆料,其特征在于:无机填料为氢氧化铝与氢氧化镁质量比为6:1~2:1的混合物,氢氧化铝和氢氧化镁的形貌均为六角片形。
9.根据权利要求1或2所述的B2级低烟无卤聚烯烃电缆料,其特征在于:炭黑母粒中炭黑的质量含量为50%,炭黑粒径为1.0~3.0μm;纳米蒙脱土表面经钛酸酯处理,纳米蒙脱土的平均粒径为1~50nm。
10.权利要求1-9任意一项所述的B2级低烟无卤聚烯烃电缆料的制备方法,其特征在于:将乙烯-丙烯酸丁酯共聚物、乙烯-乙酸乙烯酯、超低密度低密度聚乙烯、相容剂、润滑剂、抗氧剂、炭黑母粒、无机填料和纳米蒙脱土依次加入捏炼机捏练,然后经双阶机组挤出造粒;其中,捏炼机出料温度为155℃~165℃,捏炼时间为15-16min,捏炼过程中上顶栓每3min抬起一次,确保物料混合均匀;双阶机组中双螺杆和单螺杆温度设定范围均为110℃~125℃。
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