CN103937067A - 抗开裂低烟无卤光缆阻燃护套料及其制备方法 - Google Patents
抗开裂低烟无卤光缆阻燃护套料及其制备方法 Download PDFInfo
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Abstract
本发明涉及一种抗开裂低烟无卤光缆阻燃护套料及其制备方法,它的原料配方包括下列重量份数的组分:聚合物基料30~50份、阻燃剂25~45份、偶联剂0.5~2份、润滑剂1~3份、抗氧剂0.2~0.5份,聚合物基料包括高密度聚乙烯、乙烯-醋酸乙烯共聚物和茂金属合剂,它们的质量比为5~7:0.8~1.5:1,偶联剂为单烷氧基型钛酸酯,阻燃剂为氢氧化铝、氢氧化镁、硼酸锌中的一种或多种组成的混合物,其平均粒径≤3微米。一方面通过使用包含高密度聚乙烯、乙烯-醋酸乙烯共聚物和茂金属合剂的聚合物基料,提高了聚合物基料的耐热性,从而提高其在热态时的抗开裂性能;另一方面选用单烷氧基型钛酸酯类高效偶联剂和平均粒径≤3微米的阻燃剂,能够增强聚合物基料与阻燃剂的界面结合力和相容性。
Description
技术领域
本发明属于高分子材料领域,具体涉及一种抗开裂低烟无卤光缆阻燃护套料及其制备方法。
背景技术
在某些环境中敷设使用的光缆,要求具有阻燃特性。例如在地铁、隧道、石油、煤矿以及大楼、计算机房、公共建筑等场合使用的光缆。这时应采用阻燃材料制作光缆护套,特别是随着光纤到户(FTTH)的迅速发展,室内光缆尤其是皮线(接入网蝶形光缆)光缆中,必须采用阻燃护套料。阻燃护套料通常分两大类,一是阻燃聚氯乙烯(PVC)护套料,一是阻燃聚烯烃(如EVA,PE)护套料。
聚氯乙烯分子中有氯原子(卤素原子)比起聚乙烯这类纯碳氢化合物有可燃性较低的优点,聚氯乙烯护套还具有良好机械性能、抗化学反应、以及良好的环境性能,被广泛用作电缆护套料。聚氯乙烯中加入无机填料,抗氧化剂制成的阻燃料具有良好有阻燃性能,但是当阻燃PVC燃烧时产生的游离氯与空气中水分会反应生成具有强烈腐蚀性的HCl,还会产生浓重的黑烟。因此,即使是低烟低卤的阻燃PVC在燃烧时生成的黑烟和腐蚀性HCl还会带来灭火的困难和对建筑物的损害。因而最好采用低烟、无卤的阻燃聚烯烃材料作为护套料。但聚烯烃本身是易燃且延燃的物质。为了降低其可燃性,要在混合物中填充无机物,如氢氧化铝,氢氧化镁等。这些无机填料在一定温度下会熔融,其分解温度略高于护套挤出温度。在聚合物中加入无机填料后,势必降低其机械性能和挤出性能,因而可通过加入偶联剂以改善混合物的机械和挤出性能,再加上适量的抗氧剂和炭黑,即制成低烟无卤的阻燃护套料。但在大多数的低烟无卤阻燃护套料的商业产品中均存在抗开裂性差的问题。有的低烟无卤阻燃光缆,甚至还在光缆盘上即发生开裂现象,通常是线盘的最外层向阳面的光缆护套发生开裂,往往是在夏季太阳暴晒下,在光缆弯曲受力和热应力的作用下产生的开裂现象。
发明内容
本发明目的是为了克服现有技术的不足而提供一种抗开裂低烟无卤光缆阻燃护套料。
为达到上述目的,本发明所采用的技术方案为:一种抗开裂低烟无卤光缆阻燃护套料,它的原料配方包括下列重量份数的组分:聚合物基料30~50份、阻燃剂25~45份、偶联剂0.5~2份、润滑剂1~3份、抗氧剂0.2~0.5份,所述的聚合物基料包括高密度聚乙烯、乙烯-醋酸乙烯共聚物和茂金属合剂,它们的质量比为5~7:0.8~1.5:1,所述的偶联剂为单烷氧基型钛酸酯,所述的阻燃剂为氢氧化铝、氢氧化镁、硼酸锌中的一种或多种组成的混合物,其平均粒径≤3微米。
优化地,所述阻燃护套料的原料配方中还包括5~10份阻燃剂填料。
优化地,所述阻燃护套料的原料配方中还包括1.5~5份相容剂。
优化地,所述阻燃护套料的原料配方中还包括1~3份碳黑。
优化地,所述阻燃护套料的原料配方中还包括0.025~0.1份含氟流变剂。
优化地,所述的润滑剂为聚乙烯蜡、硅油、硬脂酸盐中的一种或及几种组成的混合物,所述的抗氧剂为四[β-(3,5-二叔丁基-4-羟基苯基)丙酸]季戊四醇酯、三(2.4-二叔丁基苯基)亚磷酸酯、双酚A中的一种或及几种组成的混合物。
本发明还提供一种抗开裂低烟无卤光缆阻燃护套料的制备方法,包括以下步骤:
(a)将配方量的阻燃剂、偶联剂加入混合机,在80~90℃温度下以100~300转/分的速度混合5~30分钟,随后向其中投入配方量的润滑剂、抗氧剂,以100~300转/分的速度混8~10分钟;
(b)向步骤(a)得到的物料中加入聚合物基料,以100~300转/分的速度混2~5分钟;
(c)将步骤(b)得到的物料加入到双螺杆造粒机中混炼,挤出,造粒。
优化地,所述双螺杆造粒机各区温度为:一区135~140℃、二区140~150℃、三区135~140℃、四区135~140℃、五区135~140℃、六区115~125℃、七区120~130℃、八区115~125℃、九区115~125℃、十区120~130℃、十一区130~135℃,机头温度为145~155℃,料压为20~30MPa。
优化地,所述步骤(a)中,在投入润滑剂、抗氧剂后投入阻燃剂填料。
优化地,所述步骤(b)中,相容剂、碳黑、含氟流变剂在加入聚合物基料后投入。
由于上述技术方案运用,本发明与现有技术相比具有下列优点:本发明抗开裂低烟无卤光缆阻燃护套料,一方面通过使用包含高密度聚乙烯、乙烯-醋酸乙烯共聚物和茂金属合剂的聚合物基料,提高了聚合物基料的耐热性,从而提高其在热态时的抗开裂性能;另一方面选用单烷氧基型钛酸酯类高效偶联剂和平均粒径≤3微米的阻燃剂,能够增强聚合物基料与阻燃剂的界面结合力和相容性。
具体实施方式
本发明开裂低烟无卤光缆阻燃护套料,它的原料配方包括下列重量份数的组分:聚合物基料30~50份、阻燃剂25~45份、偶联剂0.5~2份、润滑剂1~3份、抗氧剂0.2~0.5份,所述的聚合物基料包括高密度聚乙烯、乙烯-醋酸乙烯共聚物和茂金属合剂,它们的质量比为5~7:0.8~1.5:1,所述的偶联剂为单烷氧基型钛酸酯,所述的阻燃剂为氢氧化铝、氢氧化镁、硼酸锌中的一种或多种组成的混合物,其平均粒径≤3微米。一方面通过使用包含高密度聚乙烯、乙烯-醋酸乙烯共聚物和茂金属合剂的聚合物基料,提高了聚合物基料的耐热性,从而提高其在热态时的抗开裂性能;另一方面选用单烷氧基型钛酸酯类高效偶联剂和平均粒径≤3微米的阻燃剂,能够增强聚合物基料与阻燃剂的界面结合力和相容性。使用单一成分的阻燃剂一般很难满足无卤阻燃电缆料的使用要求,在本发明中,选用含有两种或两种以上成分的复配阻燃剂效果更好。例如,将氢氧化铝与氢氧化镁配合使用,可以起到协同作用,虽然氢氧化镁分解吸收的热量比氢氧化铝小,但是分解温度较高,可以达到340℃,而且氢氧化镁有促进聚合物表面成炭的作用。
在本发明中,在阻燃剂中添加如活性碳酸钙、钛白粉等小颗粒成分,能够提高阻燃剂在聚合物基料中的分散性。阻燃护套料的原料配方中还包括1.5~5份相容剂,用于降低聚合物基料中高密度聚乙烯、乙烯-醋酸乙烯共聚物和茂金属合剂间的界面张力,从而改善聚合物之间的相容性;例如,相容剂MC218是由化学接枝改性乙烯-醋酸乙烯(EVA)制得,在保持乙烯-醋酸乙烯物理性能的同时,呈现出高的极性和反应性,能够提高氢氧化铝、氢氧化镁的分散性及相容性,从而最大限度的提高电缆料的阻燃性,降低烟指数、发烟量、发热量和一氧化碳的产生量,提升氧指数,改善滴落性能等。阻燃护套料的原料配方中还包括1~3份碳黑,用以抗紫外光老化,优选为采用槽法碳黑,粒度为15~30nm或者碳黑母料形式加入混和。阻燃护套料的原料配方中还包括0.025~0.1份含氟流变剂,优选0.5~2份3M公司开发的PPA母粒(PPA在母粒中质量含量为5%,PE质量含量为95%),它可迁移到机头/熔体界面形成一层簿膜,作为机头的润滑剂,从而减小挤出压力;并且在一定的温度下,加入含氟流变剂的PE开始发生连续熔体破裂的剪切速率值远高于未加含氟流变剂的PE开始发生连续熔体破裂的剪切速率值,因而可有效地消除熔体破裂现象,降低熔体温度,提高挤出效率,并在护套表面出现鲨皮斑,使表面光亮滑爽。
在本发明中,润滑剂可以选用常规的那些,例如聚乙烯蜡、硅油、硬脂酸盐中的一种或及几种组成的混合物,抗氧剂可以选用常规的那些,例如[β-(3,5-二叔丁基-4-羟基苯基)丙酸]季戊四醇酯、三(2.4-二叔丁基苯基)亚磷酸酯、双酚A中的一种或及几种组成的混合物。
为了制备上述的抗开裂低烟无卤光缆阻燃护套料的制备方法,包括以下步骤:(a)将配方量的阻燃剂、偶联剂加入混合机,在80~90℃温度下以100~300转/分的速度混合5~30分钟,随后向其中投入配方量的润滑剂、抗氧剂,以100~300转/分的速度混8~10分钟;(b)向步骤(a)得到的物料中加入聚合物基料,以100~300转/分的速度混2~5分钟;(c)将步骤(b)得到的物料加入到双螺杆造粒机中混炼,挤出,造粒。由于无机金属氢氧化物阻燃剂的添加量会使聚合物基料的粘度增大,塑性降低,断裂伸长率下降,因此在本发明中先用偶联剂处理阻燃剂,可取得较好的效果。双螺杆造粒机各区温度优选为:一区135~140℃、二区140~150℃、三区135~140℃、四区135~140℃、五区135~140℃、六区115~125℃、七区120~130℃、八区115~125℃、九区115~125℃、十区120~130℃、十一区130~135℃,机头温度为145~155℃,料压为20~30MPa。本发明中,步骤(a)中,在投入润滑剂、抗氧剂后投入阻燃剂填料,步骤(b)中,相容剂、碳黑、含氟流变剂在加入聚合物基料后投入,这样使各种组分充分混合均匀,保持良好以塑化状态,从而提高材料的抗开裂性能。
下面对本发明优选实施方案进行详细说明。
实施例1
本例提供一种抗开裂低烟无卤光缆阻燃护套料,采用的原料具体如下:
制备方法具体如下:(a)将上述重量的阻燃剂、偶联剂加入混合机,在80℃温度下以100转/分的速度混合10分钟(每2~3分钟反向旋转),随后向其中投入上述重量的润滑剂、抗氧剂,以100转/分的速度混10分钟;
(b)向步骤(a)得到的物料中加入聚合物基料,以130转/分的速度混2分钟;
(c)将步骤(b)得到的物料加入到双螺杆造粒机中混炼,挤出,造粒。
实施例2
本例提供一种抗开裂低烟无卤光缆阻燃护套料,采用的原料具体如下:
制备方法具体如下:
(a)将上述重量的的阻燃剂、偶联剂加入混合机,在90℃温度下以130转/分的速度混合8分钟,随后向其中投入上述重量的润滑剂、抗氧剂、阻燃剂填料,以130转/分的速度混8分钟;
(b)向步骤(a)得到的物料中加入上述重量的聚合物基料、相容剂、碳黑、含氟流变剂,以130转/分的速度混3分钟;
(c)将步骤(b)得到的物料加入到双螺杆造粒机中(双螺杆造粒机各区温度为:一区135~140℃、二区140~150℃、三区135~140℃、四区135~140℃、五区135~140℃、六区115~125℃、七区120~130℃、八区115~125℃、九区115~125℃、十区120~130℃、十一区130~135℃,机头温度为145~155℃,料压为20~30MPa)混炼,挤出,造粒。
实施例3
本例提供一种抗开裂低烟无卤光缆阻燃护套料,采用的原料具体如下:
制备方法具体如下:
(a)将上述重量的的阻燃剂、偶联剂加入混合机,在80~90℃温度下以300转/分的速度混合5分钟,随后向其中投入上述重量的润滑剂、抗氧剂、阻燃剂填料,以130转/分的速度混10分钟;
(b)向步骤(a)得到的物料中加入上述重量的聚合物基料、相容剂、碳黑、含氟流变剂,以130转/分的速度混3分钟;
(c)将步骤(b)得到的物料加入到双螺杆造粒机中(双螺杆造粒机各区温度为:一区135~140℃、二区140~150℃、三区135~140℃、四区135~140℃、五区135~140℃、六区115~125℃、七区120~130℃、八区115~125℃、九区115~125℃、十区120~130℃、十一区130~135℃,机头温度为145~155℃,料压为20~30MPa)混炼,挤出,造粒。
实施例4
本例提供一种抗开裂低烟无卤光缆阻燃护套料,采用的原料具体如下:
制备方法具体如下:
(a)将上述重量的的阻燃剂、偶联剂加入混合机,在85℃温度下以130转/分的速度混合10分钟,随后向其中投入上述重量的润滑剂、抗氧剂、阻燃剂填料,以130转/分的速度混10分钟;
(b)向步骤(a)得到的物料中加入上述重量的聚合物基料、相容剂、碳黑、含氟流变剂,以130转/分的速度混3分钟;
(c)将步骤(b)得到的物料加入到双螺杆造粒机中(双螺杆造粒机各区温度为:一区135~140℃、二区140~150℃、三区135~140℃、四区135~140℃、五区135~140℃、六区115~125℃、七区120~130℃、八区115~125℃、九区115~125℃、十区120~130℃、十一区130~135℃,机头温度为145~155℃,料压为20~30MPa)混炼,挤出,造粒。
上述实施例中制备的产品性能经检测, 完全符合中华人民共和国通信行业标准 YD/T 1113-2001“光缆护套用低烟无卤阻燃材料特性” 以及中华人民共和国机械行业标准JB/T 10707-2007 “热塑性无卤低烟阻燃电缆料”的性能要求,具有良好的抗开裂性能。
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 (10)
1. 一种抗开裂低烟无卤光缆阻燃护套料,其特征在于,它的原料配方包括下列重量份数的组分:聚合物基料30~50份、阻燃剂25~45份、偶联剂0.5~2份、润滑剂1~3份、抗氧剂0.2~0.5份,所述的聚合物基料包括高密度聚乙烯、乙烯-醋酸乙烯共聚物和茂金属合剂,它们的质量比为5~7:0.8~1.5:1,所述的偶联剂为单烷氧基型钛酸酯,所述的阻燃剂为氢氧化铝、氢氧化镁、硼酸锌中的一种或多种组成的混合物,其平均粒径≤3微米。
2.根据权利要求1所述的抗开裂低烟无卤光缆阻燃护套料,其特征在于:所述阻燃护套料的原料配方中还包括5~10份阻燃剂填料。
3.根据权利要求1所述的抗开裂低烟无卤光缆阻燃护套料,其特征在于:所述阻燃护套料的原料配方中还包括1.5~5份相容剂。
4.根据权利要求1所述的抗开裂低烟无卤光缆阻燃护套料,其特征在于:所述阻燃护套料的原料配方中还包括1~3份碳黑。
5.根据权利要求1所述的抗开裂低烟无卤光缆阻燃护套料,其特征在于:所述阻燃护套料的原料配方中还包括0.025~0.1份含氟流变剂。
6.根据权利要求1所述的抗开裂低烟无卤光缆阻燃护套料,其特征在于:所述的润滑剂为聚乙烯蜡、硅油、硬脂酸盐中的一种或及几种组成的混合物,所述的抗氧剂为四[β-(3,5-二叔丁基-4-羟基苯基)丙酸]季戊四醇酯、三(2.4-二叔丁基苯基)亚磷酸酯、双酚A中的一种或及几种组成的混合物。
7.权利要求1至6中任一所述抗开裂低烟无卤光缆阻燃护套料的制备方法,其特征在于,包括以下步骤:
(a)将配方量的阻燃剂、偶联剂加入混合机,在80~90℃温度下以100~300转/分的速度混合5~30分钟,随后向其中投入配方量的润滑剂、抗氧剂,以100~300转/分的速度混8~10分钟;
(b)向步骤(a)得到的物料中加入聚合物基料,以100~300转/分的速度混2~5分钟;
(c)将步骤(b)得到的物料加入到双螺杆造粒机中混炼,挤出,造粒。
8.根据权利要求7所述的抗开裂低烟无卤光缆阻燃护套料的制备方法,其特征在于,所述双螺杆造粒机各区温度为:一区135~140℃、二区140~150℃、三区135~140℃、四区135~140℃、五区135~140℃、六区115~125℃、七区120~130℃、八区115~125℃、九区115~125℃、十区120~130℃、十一区130~135℃,机头温度为145~155℃,料压为20~30MPa。
9.根据权利要求7所述的抗开裂低烟无卤光缆阻燃护套料的制备方法,其特征在于:所述步骤(a)中,在投入润滑剂、抗氧剂后投入阻燃剂填料。
10.根据权利要求7所述的抗开裂低烟无卤光缆阻燃护套料的制备方法,其特征在于:所述步骤(b)中,相容剂、碳黑、含氟流变剂在加入聚合物基料后投入。
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