CN105602071B - 耐高温辐照无卤阻燃汽车线料及其制备方法 - Google Patents
耐高温辐照无卤阻燃汽车线料及其制备方法 Download PDFInfo
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Abstract
本发明公开了一种耐高温辐照无卤阻燃汽车线料及其制备方法,其中所述耐高温辐照无卤阻燃汽车线料采用具有不同熔融指数的高密度聚乙烯、线性低密度乙烯、热塑性聚氨酯弹性体、烯烃嵌段共聚物和乙烯‑丙烯酸丁酯共聚物为树脂基体,在上述树脂基体中添加由膨胀阻燃剂、氢氧化镁和硼酸锌复合形成的无卤阻燃剂,并结合功能性填充剂、抗氧剂、润滑剂和交联敏化剂,所得的汽车线料既能满足所需的柔软度、耐磨性,又能保证产品热过载性能,此外该线材阻燃性能优良,低烟无卤,符合环保要求,且该产品的制备方法工艺简单、操作容易、成本低,适于推广使用。
Description
技术领域
本发明涉及一种阻燃复合物及其制备方法,尤其涉及一种耐高温辐照无卤阻燃汽车线料及其制备方法,属于高分子复合材料技术领域。
背景技术
众所周知,汽车线束材料需要有阻燃性、耐磨性、耐油性等性能要求。而根据不同的环境和使用位置,汽车电缆又可分为80℃,105℃,125℃和150℃各种温度等级,其中耐高温125℃以上的材料因其既要满足耐高温特点,又要同时具备耐磨、阻燃等特性,目前市场上均采用低烟低卤材料。而低烟低卤产品中所采用的阻燃剂多为溴类阻燃剂,其燃烧将产生大量的烟雾以及刺激性气体,对环境造成莫大的伤害。随着环保观念的深入人心,上述汽车电缆材料已不能满足当前社会发展的需要,因此如何提供一种既低烟无卤满足环保要求又同时能够满足汽车耐高温电缆所需要特性的材料,成为当前亟待解决的问题。
发明内容
为了克服上述现有技术中存在的不足,本发明提供了一种耐高温辐照无卤阻燃汽车线料及其制备方法,该制备方法能够高速挤出,且制备所得的汽车线料环保无卤,能够满足汽车线料的要求,且各项性能优异。
本发明为了解决其技术问题所采用的技术方案是:
一种耐高温辐照无卤阻燃汽车线料,由下述按重量份计的各组分组成:
其中:
所述高密度聚乙烯的熔融指数为0.3~1.0g/min;
所述线性低密度聚乙烯的熔融指数为10~20g/min;
所述热塑性聚氨酯弹性体的邵氏A硬度为80~90;
所述烯烃嵌段共聚物的熔融指数为1.5~5.0g/min;
所述乙烯-丙烯酸丁酯共聚物的熔融指数为3~8g/min;
所述阻燃剂由膨胀阻燃剂、氢氧化镁和硼酸锌按照重量比为1:0.3~1.5:0.1~0.8混合形成;
所述交联敏化剂为多官能团的丙烯酸酯。
本发明进一步的技术方案是:
所述功能性填充剂为纳米二氧化硅和改性纳米高岭土中的至少一种,且该功能性填充剂的粒径为100~500nm;其中所述改性纳米高岭土为采用硅烷偶联剂进行表面改性的纳米高岭土,且所述硅烷偶联剂的用量为纳米高岭土用量的1~2%。
所述功能性填充剂为纳米二氧化硅和改性纳米高岭土按照重量比为1:1~2混合形成。
所述多官能团的丙烯酸酯为三烯丙基异氰脲酸酯(TAIC)和三甲基丙烯酸三羟甲基丙酯(TMPTMA)中的一种。
所述抗氧剂由必需抗氧剂和非必需抗氧剂组成,其中所述必需抗氧剂为抗氧剂300、抗氧剂1024和抗氧剂1035形成的混合物,非必需抗氧剂为抗氧剂DLTP和抗氧剂1010中的至少一种。
所述必需抗氧剂和非必需抗氧剂的重量比为2.8~9:3,且必需抗氧剂中抗氧剂300、抗氧剂1024和抗氧剂1035的重量比为0.8~1:1~1.5:0.8~1.2。
所述润滑剂为接枝蜡与选自聚乙烯蜡、氧化聚乙烯蜡及硅酮母粒中的至少两种的组合,且接枝蜡占润滑剂的重量比例不低于50%。
所述接枝蜡为马来酸酐接枝聚乙烯蜡。
本发明还公开了一种上述的耐高温辐照无卤阻燃汽车线料的制备方法,包括下述步骤:
(1)按配方用量将高密度聚乙烯、线性低密度聚乙烯、热塑性聚氨酯弹性体、烯烃嵌段共聚物、乙烯-丙烯酸丁酯共聚物、阻燃剂、功能性填充剂、抗氧剂、润滑剂和交联敏化剂加入高速搅拌机中,并采用500~800rpm的转速将上述原料搅拌混合均匀得到混合原料;
(2)将步骤(1)中所得混合原料转入密炼机中进行密炼得到密炼混合物;其中密炼的温度为165~175℃;
(3)将步骤(2)中所得密炼混合物依次经双螺杆混炼和单螺杆挤出造粒,得到耐高温辐照无卤阻燃汽车线料;其中螺杆温度为140~160℃,熔融段温度为170~190℃,模头温度为195~205℃;其中双螺杆的长径比为1:40~50,且单螺杆的模头采用40~80/120~150/60~80目的三层式复合过滤网。
本发明还公开了一种上述耐高温辐照无卤阻燃汽车线料制备形成的汽车电缆。
本发明的有益技术效果是:本发明所述耐高温辐照无卤阻燃汽车线料采用具有不同熔融指数的高密度聚乙烯、线性低密度乙烯、热塑性聚氨酯弹性体、烯烃嵌段共聚物和乙烯-丙烯酸丁酯共聚物为树脂基体,在上述树脂基体中添加由膨胀阻燃剂、氢氧化镁和硼酸锌复合形成的无卤阻燃剂,并结合功能性填充剂、抗氧剂、润滑剂和交联敏化剂,所得的汽车线料既能满足所需的柔软度、耐磨性,又能保证产品热过载性能,此外该线材阻燃性能优良,低烟无卤,符合环保要求,且该产品的制备方法工艺简单、操作容易、成本低,适于推广使用。
具体实施方式
下面结合具体实施例1~5和对比实施例1对本发明进行详细说明,且下述具体实施例中所采用的原料均为市面所售产品,未提及的操作方法及所使用的设备均为本领域常规操作方法和常规设备,为本领域技术人员能够获知的内容。
下述具体实施例中所采用的改性纳米高岭土为采用硅烷偶联剂进行表面硅烷化改性的纳米高岭土,硅烷偶联剂采用本领域常规硅烷偶联剂,且硅烷偶联剂的用量为纳米高岭土用量的质量百分比的1~2%;接枝蜡为马来酸酐接枝聚乙烯蜡。
具体实施例1
本实施例提供一种耐高温辐照无卤阻燃汽车线料A,其原料配方参见表1,其中:
高密度聚乙烯的熔融指数为0.3g/min;线性低密度聚乙烯的熔融指数为20g/min;热塑性聚氨酯弹性体的邵氏A硬度为90;烯烃嵌段共聚物的熔融指数为5.0g/min;乙烯-丙烯酸丁酯共聚物的熔融指数为5g/min;阻燃剂由膨胀阻燃剂、氢氧化镁和硼酸锌按照重量比为1:1.4:0.8混合形成;功能性填充剂改性纳米高岭土,且该改性纳米高岭土粒径为200nm;抗氧剂由抗氧剂300、抗氧剂1024、抗氧剂1035和抗氧剂DLTP按照重量比为1.0:1.5:1.0:1.5;润滑剂为接枝蜡和氧化聚乙烯蜡混合形成,且接枝蜡占润滑剂的重量比例为80%;交联敏化剂为TMPTMA。
上述耐高温辐照无卤阻燃汽车线料A的制备方法如下所述:
(1)按配方用量将高密度聚乙烯、线性低密度聚乙烯、热塑性聚氨酯弹性体、烯烃嵌段共聚物、乙烯-丙烯酸丁酯共聚物、阻燃剂、功能性填充剂、抗氧剂、润滑剂和交联敏化剂加入高速搅拌机中,并采用500~800rpm的转速将上述原料搅拌混合均匀得到混合原料;
(2)将(1)中所得混合原料转入密炼机中进行密炼得到密炼混合物;其中密炼的温度为165~175℃;
(3)将步骤(2)中所得密炼混合物依次经双螺杆混炼和单螺杆挤出造粒,得到耐高温辐照无卤阻燃汽车线料;其中螺杆温度为140~160℃,熔融段温度为170~190℃,模头温度为195~205℃;其中双螺杆的长径比为1:40~50,且单螺杆的模
头采用40~80/120~150/60~80目的三层式复合过滤网。
具体实施例2
本实施例提供一种耐高温辐照无卤阻燃汽车线料B,其原料配方参见表1,其中:
高密度聚乙烯的熔融指数为0.5g/min;线性低密度聚乙烯的熔融指数为15g/min;热塑性聚氨酯弹性体的邵氏A硬度为88;烯烃嵌段共聚物的熔融指数为3.5g/min;乙烯-丙烯酸丁酯共聚物的熔融指数为5g/min;阻燃剂由膨胀阻燃剂、氢氧化镁和硼酸锌按照重量比为1:0.8:0.5混合形成;功能性填充剂为纳米二氧化硅和改性纳米高岭土按重量比为1:2混合形成,且纳米二氧化硅粒径为200nm,改性纳米高岭土粒径为500nm;抗氧剂由抗氧剂300、抗氧剂1024、抗氧剂1035和抗氧剂1010按照重量比为1.0:1.0:1.2:1.2;润滑剂为接枝蜡和聚乙烯蜡混合形成,且接枝蜡占润滑剂的重量比例为60%;交联敏化剂为TAIC。
上述耐高温辐照无卤阻燃汽车线料B的制备方法参照具体实施例1中所述。
具体实施例3
本实施例提供一种耐高温辐照无卤阻燃汽车线料C,其原料配方参见表1,其中:
高密度聚乙烯的熔融指数为0.7g/min;线性低密度聚乙烯的熔融指数为18g/min;热塑性聚氨酯弹性体的邵氏A硬度为85;烯烃嵌段共聚物的熔融指数为2.5g/min;乙烯-丙烯酸丁酯共聚物的熔融指数为8g/min;阻燃剂由膨胀阻燃剂、氢氧化镁和硼酸锌按照重量比为1:0.4:0.3混合形成;功能性填充剂为纳米二氧化硅,且纳米二氧化硅粒径为100nm;抗氧剂由抗氧剂300、抗氧剂1024、抗氧剂1035、抗氧剂DLTP和抗氧剂1010按照重量比为0.8:1.2:0.8:1.5:1.5;润滑剂为接枝蜡和硅酮母粒混合形成,且接枝蜡占润滑剂的重量比例为55%;交联敏化剂为TAIC。
上述耐高温辐照无卤阻燃汽车线料C的制备方法如具体实施例1中所述。
具体实施例4
本实施例提供一种耐高温辐照无卤阻燃汽车线料D,其原料配方参见表1,其中:
高密度聚乙烯的熔融指数为1.0g/min;线性低密度聚乙烯的熔融指数为10g/min;热塑性聚氨酯弹性体的邵氏A硬度为80;烯烃嵌段共聚物的熔融指数为1.5g/min;乙烯-丙烯酸丁酯共聚物的熔融指数为5g/min;阻燃剂由膨胀阻燃剂、氢氧化镁和硼酸锌按照重量比为1:0.5:0.2混合形成;功能性填充剂为改性纳米高岭土,且该改性纳米高岭土粒径为300nm;抗氧剂由抗氧剂300、抗氧剂1024、抗氧剂1035和抗氧剂1010按照重量比为1.0:1.0:1.0:1.0;润滑剂为接枝蜡、聚乙烯蜡和氧化聚乙烯蜡混合形成,且接枝蜡占润滑剂的重量比例为60%;交联敏化剂为TMPTMA。
上述耐高温辐照无卤阻燃汽车线料D的制备方法如具体实施例1中所述。
具体实施例5
本实施例提供一种耐高温辐照无卤阻燃汽车线料E,其原料配方参见表1,其中:
高密度聚乙烯的熔融指数为1.0g/min;线性低密度聚乙烯的熔融指数为10g/min;热塑性聚氨酯弹性体的邵氏A硬度为90;烯烃嵌段共聚物的熔融指数为2.5g/min;乙烯-丙烯酸丁酯共聚物的熔融指数为3g/min;阻燃剂由膨胀阻燃剂、氢氧化镁和硼酸锌按照重量比为1:0.5:0.2混合形成;功能性填充剂为纳米二氧化硅和改性纳米高岭土按重量比为1:1混合形成,且纳米二氧化硅粒径为400nm,改性纳米高岭土粒径为450nm;抗氧剂由抗氧剂300、抗氧剂1024、抗氧剂1035和抗氧剂1010按照重量比为0.8:1.0:1.0:1.2;润滑剂为接枝蜡和聚乙烯蜡混合形成,且接枝蜡占润滑剂的重量比例为70%;交联敏化剂为TMPTMA。
上述耐高温辐照无卤阻燃汽车线料E的制备方法如具体实施例1中所述。
表1为实施例1~5的原料组成
对上述具体实施例1~5制备所得的汽车线料的各项性能进行测试,所采用的测试标准参照国际相关测试标准(IEC60811,ISO4589等),测试标准具体内容为本领域技术人员可获知的,因此不再赘述,测试结果参见表2。
表2具体实施例1~5耐高温热塑性阻燃材料性能
以上对本发明做了详尽的描述,其目的在于让熟悉此领域技术的人士能够了解本发明的内容并加以实施,并不能以此限制本发明的保护范围,且本发明不限于上述的实施例,凡根据本发明的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。
Claims (9)
1.一种耐高温辐照无卤阻燃汽车线料,其特征在于:由下述按重量份计的各组分组成:
其中:
所述高密度聚乙烯的熔融指数为0.3~1.0g/min;
所述线性低密度聚乙烯的熔融指数为10~20g/min;
所述热塑性聚氨酯弹性体的邵氏A硬度为80~90;
所述烯烃嵌段共聚物的熔融指数为1.5~5.0g/min;
所述乙烯-丙烯酸丁酯共聚物的熔融指数为3~8g/min;
所述阻燃剂由膨胀阻燃剂、氢氧化镁和硼酸锌按照重量比为1:0.3~1.5:0.1~0.8混合形成;
所述交联敏化剂为多官能团的丙烯酸酯。
2.根据权利要求1所述的耐高温辐照无卤阻燃汽车线料,其特征在于:所述功能性填充剂为纳米二氧化硅和改性纳米高岭土中的至少一种,且该功能性填充剂的粒径为100~500nm;其中所述改性纳米高岭土为采用硅烷偶联剂进行表面改性的纳米高岭土,且所述硅烷偶联剂的用量为纳米高岭土用量的1~2%。
3.根据权利要求2所述的耐高温辐照无卤阻燃汽车线料,其特征在于:所述功能性填充剂为纳米二氧化硅和改性纳米高岭土按照重量比为1:1~2混合形成。
4.根据权利要求1所述的耐高温辐照无卤阻燃汽车线料,其特征在于:所述多官能团的丙烯酸酯为三甲基丙烯酸三羟甲基丙酯。
5.根据权利要求1所述的耐高温辐照无卤阻燃汽车线料,其特征在于:所述抗氧剂由必需抗氧剂和非必需抗氧剂组成,其中所述必需抗氧剂为抗氧剂300、抗氧剂1024和抗氧剂1035形成的混合物,非必需抗氧剂为抗氧剂DLTP和抗氧剂1010中的至少一种。
6.根据权利要求5所述的耐高温辐照无卤阻燃汽车线料,其特征在于:所述必需抗氧剂和非必需抗氧剂的重量比为2.8~9:3,且必需抗氧剂中抗氧剂300、抗氧剂1024和抗氧剂1035的重量比为0.8~1:1~1.5:0.8~1.2。
7.根据权利要求1所述的耐高温辐照无卤阻燃汽车线料,其特征在于:所述润滑剂为接枝蜡与选自聚乙烯蜡、氧化聚乙烯蜡及硅酮母粒中的至少两种的组合,且接枝蜡占润滑剂的重量比例不低于50%。
8.根据权利要求7所述的耐高温辐照无卤阻燃汽车线料,其特征在于:所述接枝蜡为马来酸酐接枝聚乙烯蜡。
9.一种根据权利要求1至8中任一权利要求所述的耐高温辐照无卤阻燃汽车线料制备形成的汽车电缆。
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CN104788799A (zh) * | 2015-04-21 | 2015-07-22 | 江苏德威新材料股份有限公司 | 环保型无卤电动汽车传导充电系统用电缆护套料及其制备方法 |
CN105086161A (zh) * | 2015-08-28 | 2015-11-25 | 广州敬信高聚物科技有限公司 | 一种新型无卤阻燃复合材料及其制备方法 |
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