CN113462073A - 一种无卤阻燃物理发泡绝缘料及其制备方法 - Google Patents
一种无卤阻燃物理发泡绝缘料及其制备方法 Download PDFInfo
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Abstract
本发明公开了一种无卤阻燃物理发泡绝缘料,包括如下重量份的组分:预辐照的聚烯烃组合物40份‑60份;改性多晶莫来石纤维5份‑12份;单甘酯3份‑8份;含酸酐的低介电树脂1份‑5份;聚砜1份‑5份;交联剂3份‑8份。本发明通过预辐照的方法,对聚烯烃组合物进行改性,以改变其与其他物质的相容性,再通过对多晶莫来石纤维的改性,使得多晶莫来石纤维能够很好地分散在预辐照后的聚烯烃组合物中,以增加绝缘料的阻燃性能,同时,由于聚烯烃组合物由聚丙烯、聚1‑丁烯、聚4‑甲基‑1‑戊烯、己内酯改性甲基丙烯酸酯组成,使得聚烯烃组合物具有较好的耐热性能,适用于耐热等级高的电线电缆。
Description
技术领域
本发明涉及塑料技术领域,尤其涉及一种无卤阻燃物理发泡绝缘料及其制备方法。
背景技术
随着经济的迅速发展,电线电缆在各个行业领域中都得到广泛的应用。随着电气火灾事故的频繁发生,电线电缆的阻燃问题逐渐引起世界各国的重视。近年来,人们发现火灾事故中的人员致死原因80%以上与材料产生的浓烟和有毒气体有关,为了降低安全隐患,目前在许多大型公共场所,对专供传输电能和通讯信号使用的电线电缆,不仅要求其可以阻止火焰蔓延,还要可以维持电缆继续传输电能和通讯信号,而且在燃烧时还应具有低发烟量,产生气体腐蚀性低,利于工作人员安全撤离现场,即应使电缆具有无卤、低烟、阻燃等性能。
聚烯烃是烯烃的聚合物,由乙烯、丙烯、1-丁烯、1-戊烯、1-己烯、1-辛烯、4-甲基-1-戊烯等α-烯烃以及某些环烯烃单独聚合或共聚合而得到的一类热塑性树脂的总称,各聚合物都有其各自独特的性能优势和应用领域。但由于各材料之间的化学结构、结晶行为等的差别,导致聚合物间以及聚合物与其他成分的相容性极差。
专利CN106519409B公开了一种辐照交联低烟无卤阻燃电缆材料,其采用乙烯-醋酸乙烯共聚物、聚乙烯、相容剂、无机阻燃剂、金属氧化物、改性剂、硅酮粉、乙撑双硬脂酰胺和抗氧剂,专利CN107722439A公开了一种环保型电缆绝缘层,其外绝缘层采用乙烯-醋酸乙烯共聚物、线性低密度聚乙烯、三元乙丙橡胶、耐刮剂、敏化剂、硅氮阻燃剂、复配型防老剂、补强填充剂和复配型相容剂。上述专利中均通过添加相容剂,以增加聚烯烃与其他成分的相容性。
发明内容
为了克服现有技术的不足,本发明的目的之一在于提供一种无卤阻燃物理发泡绝缘料,其具有较好的阻燃性,耐热性好,适用于耐热等级高的电线电缆。
本发明的目的之二在于提供一种无卤阻燃物理发泡绝缘料的制备方法,其简单、易于控制,可应用于大规模生产。
本发明的目的之一采用如下技术方案实现:
一种无卤阻燃物理发泡绝缘料,包括如下重量份的组分:
预辐照的聚烯烃组合物40份-60份;改性多晶莫来石纤维5份-12份;单甘酯3份-8份;含酸酐的低介电树脂1份-5份;聚砜1份-5份;交联剂3份-8份;
其中,预辐照的聚烯烃组合物由聚丙烯、聚1-丁烯、聚4-甲基-1-戊烯、己内酯改性甲基丙烯酸酯组成。
进一步地,所述聚丙烯、聚1-丁烯、聚4-甲基-1-戊烯、己内酯改性甲基丙烯酸酯的质量比为1:(0.2-0.4):(0.1-0.3):0.2。其制备方法为:将聚丙烯、聚1-丁烯、聚4-甲基-1-戊烯、己内酯改性甲基丙烯酸酯按配方量混合均匀,然后在20kGy-40kGy的电子辐照下,进行预辐照反应,即得。聚丙烯是一种结晶的具有较高强度的材料和较好的耐热性;聚1-丁烯的耐化学性、耐老化性和电绝缘性均与聚丙烯相近;聚4-甲基-1-戊烯是密度最小的热塑性树脂,耐热性优越,熔点240℃,具有较好的电气绝缘性和耐化学药品性;己内酯改性甲基丙烯酸酯是在130℃-150℃下,以甲基丙烯酸羟乙酯为起始剂,己内酯单体以质量比1:(0.5-0.8)为聚合而成的大分子单体,其具有较好的耐刮性、耐磨耗性、低温韧性、高弹性的特性,将己内酯改性甲基丙烯酸酯添加到聚烯烃的辐照交联反应中,以对聚烯烃进行改性,使其产物表面具有酯基,能够与其他成分相容。优选地,所述聚丙烯、聚1-丁烯、聚4-甲基-1-戊烯、己内酯改性甲基丙烯酸酯的质量比为1:0.3:0.1:0.2。
进一步地,所述改性多晶莫来石纤维为带有羟基的多晶莫来石纤维,其直径为1-3μm,长度为20mm-40mm,由于其表面带有羟基,使得多晶莫来石纤维能够与预辐照的聚烯烃组合物具有较好的相容性。所述改性多晶莫来石纤维的改性方法为:采用质量比为1:2的高锰酸钾和双氧水组成的强氧化溶液,对多晶莫来石纤维进行羟基化处理,使多晶莫来石纤维表面带有羟基官能团,其中,强氧化溶液与多晶莫来石纤维的质量比为1:(50-80)。多晶莫来石纤维是一种优异的超轻质高温耐火纤维和复合材料的增强材料,是整个Al2O3-SiO2系陶瓷纤维中的一种,由莫来石微晶体构成,集晶体材料和纤维材料特性于一体,使用温度在1500℃-1700℃,高出玻璃态纤维200℃-400℃,具有耐高温、耐腐蚀、比重小、熔点高、抗热震性好、热导率低和高温强度大等优点。
进一步地,所述单甘酯为分子蒸馏单甘酯,其经分子蒸馏技术提纯所得,在树脂内迁移快,效时长,能降低表面电阻,减小静电形成和积聚。
进一步地,所述含酸酐的低介电树脂为马来酸酐接枝改性聚酰亚胺树脂,其在10GHz的频率下的介电常数小于3。聚酰亚胺树脂具有耐热耐低温、机械性能优异、加工性能好、无毒性等等特点,但其与极性聚合物的相容性较差,通过马来酸酐的接枝改性后,能够增加其与极性聚合物的相容性,使其能够更好地分散,便于后期在电子辐照的过程中的进一步反应。优选地,马来酸酐接枝改性聚酰亚胺树脂的接枝率为20%-40%。
进一步地,所述交联剂为三甲基丙烯酸三羟甲基丙烷酯、三丙烯酸三羟甲基丙烷酯中的一种或者组合。
进一步地,所述预辐照的聚烯烃组合物、聚砜、交联剂的质量比为1:(0.05-0.1):0.1。聚砜的热变形温度为175℃,可在-100℃~150℃之间长期使用,而且在高温下耐老化性能极好,可以与聚烯烃组合物发生反应,以提高其热稳定性。优选地,所述预辐照的聚烯烃组合物、聚砜、交联剂的质量比为1:0.08:0.1。
本发明的目的之一采用如下技术方案实现:
一种无卤阻燃物理发泡绝缘料,包括如下制备步骤:
S1:先预辐照的聚烯烃组合物、改性多晶莫来石纤维、含酸酐的低介电树脂、聚砜在常温下搅拌均匀,得到第一预混料;
S2:向第一预混料中加入交联剂、单甘酯,混合均匀,得到第二预混料;
S3:将第二预混料放入挤出机中,进行挤出造粒,即得无卤阻燃物理发泡绝缘料。
进一步地,在步骤S3中,挤出温度为150℃-180℃。
使用时,该无卤阻燃物理发泡绝缘料可在辐照剂量为130kGy-180kGy的电子辐照下,使其完成交联。
相比现有技术,本发明的有益效果在于:
本发明的无卤阻燃物理发泡绝缘料通过预辐照的方法,对聚烯烃组合物进行改性,以改变其与其他物质的相容性,再通过对多晶莫来石纤维的改性,使得多晶莫来石纤维能够很好地分散在预辐照后的聚烯烃组合物中,以增加绝缘料的阻燃性能,同时,由于聚烯烃组合物由聚丙烯、聚1-丁烯、聚4-甲基-1-戊烯、己内酯改性甲基丙烯酸酯组成,使得聚烯烃组合物具有较好的耐热性能,适用于耐热等级高的电线电缆。
本发明的制备方法简单、易于控制,可应用于大规模生产。
具体实施方式
下面,结合具体实施方式,对本发明做进一步描述,需要说明的是,在不相冲突的前提下,以下描述的各实施例之间或各技术特征之间可以任意组合形成新的实施例。以下是本发明具体的实施例,在下述实施例中所采用的原材料、设备等除特殊限定外均可以通过购买方式获得。以下实施例中除特殊限定外,所述改性多晶莫来石纤维为本发明所记载的方法所得的带有羟基的多晶莫来石纤维;所述单甘酯为分子蒸馏单甘酯。
实施例1:
一种无卤阻燃物理发泡绝缘料,包括如下重量份的组分:
预辐照的聚烯烃组合物40份;改性多晶莫来石纤维5份;单甘酯3份;含酸酐的低介电树脂1份;聚砜1份;交联剂3份;
其中,预辐照的聚烯烃组合物由质量比为1:0.3:0.1:0.2的聚丙烯、聚1-丁烯、聚4-甲基-1-戊烯、己内酯改性甲基丙烯酸酯组成;含酸酐的低介电树脂是接枝率为20%的马来酸酐接枝改性聚酰亚胺树脂;所述交联剂为三甲基丙烯酸三羟甲基丙烷酯。
该无卤阻燃物理发泡绝缘料,包括如下制备步骤:
S1:先预辐照的聚烯烃组合物、改性多晶莫来石纤维、含酸酐的低介电树脂、聚砜在常温下搅拌均匀,得到第一预混料;
S2:向第一预混料中加入交联剂、单甘酯,混合均匀,得到第二预混料;
S3:将第二预混料放入挤出机中,进行挤出造粒,挤出温度为160℃,即得无卤阻燃物理发泡绝缘料。
实施例2:
一种无卤阻燃物理发泡绝缘料,包括如下重量份的组分:
预辐照的聚烯烃组合物50份;改性多晶莫来石纤维8份;单甘酯5份;含酸酐的低介电树脂3份;聚砜3份;交联剂5份;
其中,预辐照的聚烯烃组合物由质量比为1:0.3:0.1:0.2的聚丙烯、聚1-丁烯、聚4-甲基-1-戊烯、己内酯改性甲基丙烯酸酯组成;含酸酐的低介电树脂是接枝率为20%的马来酸酐接枝改性聚酰亚胺树脂;所述交联剂为三甲基丙烯酸三羟甲基丙烷酯。
该无卤阻燃物理发泡绝缘料,包括如下制备步骤:
S1:先预辐照的聚烯烃组合物、改性多晶莫来石纤维、含酸酐的低介电树脂、聚砜在常温下搅拌均匀,得到第一预混料;
S2:向第一预混料中加入交联剂、单甘酯,混合均匀,得到第二预混料;
S3:将第二预混料放入挤出机中,进行挤出造粒,挤出温度为160℃,即得无卤阻燃物理发泡绝缘料。
实施例3:
一种无卤阻燃物理发泡绝缘料,包括如下重量份的组分:
预辐照的聚烯烃组合物60份;改性多晶莫来石纤维12份;单甘酯8份;含酸酐的低介电树脂5份;聚砜5份;交联剂8份;
其中,预辐照的聚烯烃组合物由质量比为1:0.3:0.1:0.2的聚丙烯、聚1-丁烯、聚4-甲基-1-戊烯、己内酯改性甲基丙烯酸酯组成;含酸酐的低介电树脂是接枝率为20%的马来酸酐接枝改性聚酰亚胺树脂;所述交联剂为三甲基丙烯酸三羟甲基丙烷酯。
该无卤阻燃物理发泡绝缘料,包括如下制备步骤:
S1:先预辐照的聚烯烃组合物、改性多晶莫来石纤维、含酸酐的低介电树脂、聚砜在常温下搅拌均匀,得到第一预混料;
S2:向第一预混料中加入交联剂、单甘酯,混合均匀,得到第二预混料;
S3:将第二预混料放入挤出机中,进行挤出造粒,挤出温度为160℃,即得无卤阻燃物理发泡绝缘料。
实施例4:
一种无卤阻燃物理发泡绝缘料,包括如下重量份的组分:
预辐照的聚烯烃组合物55份;改性多晶莫来石纤维6份;单甘酯3份;含酸酐的低介电树脂2份;聚砜4.4份;交联剂5.5份;
其中,预辐照的聚烯烃组合物由质量比为1:0.3:0.1:0.2的聚丙烯、聚1-丁烯、聚4-甲基-1-戊烯、己内酯改性甲基丙烯酸酯组成;含酸酐的低介电树脂是接枝率为20%的马来酸酐接枝改性聚酰亚胺树脂;所述交联剂为三甲基丙烯酸三羟甲基丙烷酯。
该无卤阻燃物理发泡绝缘料,包括如下制备步骤:
S1:先预辐照的聚烯烃组合物、改性多晶莫来石纤维、含酸酐的低介电树脂、聚砜在常温下搅拌均匀,得到第一预混料;
S2:向第一预混料中加入交联剂、单甘酯,混合均匀,得到第二预混料;
S3:将第二预混料放入挤出机中,进行挤出造粒,挤出温度为160℃,即得无卤阻燃物理发泡绝缘料。
实施例5:
与实施例4不同的是,实施例5的聚丙烯、聚1-丁烯、聚4-甲基-1-戊烯、己内酯改性甲基丙烯酸酯的质量比为1:0.3:0.3:0.2,具体的如下:
一种无卤阻燃物理发泡绝缘料,包括如下重量份的组分:
预辐照的聚烯烃组合物40份-60份;改性多晶莫来石纤维5份-12份;单甘酯3份-8份;含酸酐的低介电树脂1份-5份;聚砜1份-5份;交联剂3份-8份;
其中,预辐照的聚烯烃组合物由质量比为1:0.3:0.3:0.2的聚丙烯、聚1-丁烯、聚4-甲基-1-戊烯、己内酯改性甲基丙烯酸酯组成;含酸酐的低介电树脂是接枝率为20%的马来酸酐接枝改性聚酰亚胺树脂;所述交联剂为三甲基丙烯酸三羟甲基丙烷酯。
该无卤阻燃物理发泡绝缘料,包括如下制备步骤:
S1:先预辐照的聚烯烃组合物、改性多晶莫来石纤维、含酸酐的低介电树脂、聚砜在常温下搅拌均匀,得到第一预混料;
S2:向第一预混料中加入交联剂、单甘酯,混合均匀,得到第二预混料;
S3:将第二预混料放入挤出机中,进行挤出造粒,挤出温度为160℃,即得无卤阻燃物理发泡绝缘料。
实施例6:
与实施例4不同的是,实施例6的聚丙烯、聚1-丁烯、聚4-甲基-1-戊烯、己内酯改性甲基丙烯酸酯的质量比为1:0.2:0.1:0.2,具体的如下:
一种无卤阻燃物理发泡绝缘料,包括如下重量份的组分:
预辐照的聚烯烃组合物40份-60份;改性多晶莫来石纤维5份-12份;单甘酯3份-8份;含酸酐的低介电树脂1份-5份;聚砜1份-5份;交联剂3份-8份;
其中,预辐照的聚烯烃组合物由质量比为1:0.2:0.1:0.2的聚丙烯、聚1-丁烯、聚4-甲基-1-戊烯、己内酯改性甲基丙烯酸酯组成;含酸酐的低介电树脂是接枝率为20%的马来酸酐接枝改性聚酰亚胺树脂;所述交联剂为三甲基丙烯酸三羟甲基丙烷酯。
该无卤阻燃物理发泡绝缘料,包括如下制备步骤:
S1:先预辐照的聚烯烃组合物、改性多晶莫来石纤维、含酸酐的低介电树脂、聚砜在常温下搅拌均匀,得到第一预混料;
S2:向第一预混料中加入交联剂、单甘酯,混合均匀,得到第二预混料;
S3:将第二预混料放入挤出机中,进行挤出造粒,挤出温度为160℃,即得无卤阻燃物理发泡绝缘料。
以上实施例中,各材料不限于上述所述的组分,各材料还可以为本发明所记载的其它单个组分或者多种组分组成,并且各材料的组分份数不限于上述份数,各材料的组分份数还可以为本发明所记载的其它组分份数的组合,在此不再赘述。
对比例1
与实施例4相比,对比例1的聚烯烃组合物中不加入己内酯改性甲基丙烯酸酯,其余配方和制备方法与实施例1相同。
对比例2
与实施例4相比,对比例2的聚烯烃组合物中不加入聚4-甲基-1-戊烯,其余配方和制备方法与实施例1相同。
对比例3
与实施例4相比,对比例3中不加入改性多晶莫来石纤维,而且加入了多晶莫来石纤维,其余配方和制备方法与实施例1相同。
对比例4
与实施例4相比,对比例4中不加入聚砜,其余配方和制备方法与实施例1相同。
性能测试
将上述实施例1-6和对比例1-4所制得的绝缘料,在辐照剂量为160kGy的电子辐照下,进行发泡交联,所得的片材,再进行如下性能测试,拉伸强度GB/T0403-2006,断裂伸长率GB/T0403-2006,20℃时体积电阻率GB/T3048-2007,热延伸试验GB/T2951-2008,热老化试验GB/T2951-2008,烟密度试验GB8323-2008,卤酸气体试验GB/T176501-1998,结果如下所示。
表1
上述实施方式仅为本发明的优选实施方式,不能以此来限定本发明保护的范围,本领域的技术人员在本发明的基础上所做的任何非实质性的变化及替换均属于本发明所要求保护的范围。
Claims (10)
1.一种无卤阻燃物理发泡绝缘料,其特征在于,包括如下重量份的组分:
预辐照的聚烯烃组合物40份-60份;改性多晶莫来石纤维5份-12份;单甘酯3份-8份;含酸酐的低介电树脂1份-5份;聚砜1份-5份;交联剂3份-8份;
其中,预辐照的聚烯烃组合物由聚丙烯、聚1-丁烯、聚4-甲基-1-戊烯、己内酯改性甲基丙烯酸酯组成。
2.根据权利要求1所述的无卤阻燃物理发泡绝缘料,其特征在于,所述聚丙烯、聚1-丁烯、聚4-甲基-1-戊烯、己内酯改性甲基丙烯酸酯的质量比为1:(0.2-0.4):(0.1-0.3):0.2。
3.根据权利要求1所述的无卤阻燃物理发泡绝缘料,其特征在于,所述预辐照的聚烯烃组合物的制备为:将聚丙烯、聚1-丁烯、聚4-甲基-1-戊烯、己内酯改性甲基丙烯酸酯混合均匀,然后在20kGy-40kGy的电子辐照下,进行预辐照反应,即得。
4.根据权利要求1所述的无卤阻燃物理发泡绝缘料,其特征在于,所述改性多晶莫来石纤维为带有羟基的多晶莫来石纤维。
5.根据权利要求1所述的无卤阻燃物理发泡绝缘料,其特征在于,所述单甘酯为分子蒸馏单甘酯。
6.根据权利要求1所述的无卤阻燃物理发泡绝缘料,其特征在于,所述含酸酐的低介电树脂为马来酸酐接枝改性聚酰亚胺树脂,所述马来酸酐接枝改性聚酰亚胺树脂的接枝率为20%-40%。
7.根据权利要求1所述的无卤阻燃物理发泡绝缘料,其特征在于,所述交联剂为三甲基丙烯酸三羟甲基丙烷酯、三丙烯酸三羟甲基丙烷酯中的一种或者组合。
8.根据权利要求1所述的无卤阻燃物理发泡绝缘料,其特征在于,所述预辐照的聚烯烃组合物、聚砜、交联剂的质量比为1:(0.05-0.1):0.1。
9.一种如权利要求1-8任一项所述的无卤阻燃物理发泡绝缘料,其特征在于,包括如下制备步骤:
S1:先预辐照的聚烯烃组合物、改性多晶莫来石纤维、含酸酐的低介电树脂、聚砜在常温下搅拌均匀,得到第一预混料;
S2:向第一预混料中加入交联剂、单甘酯,混合均匀,得到第二预混料;
S3:将第二预混料放入挤出机中,进行挤出造粒,即得无卤阻燃物理发泡绝缘料。
10.根据权利要求1所述的无卤阻燃物理发泡绝缘料,其特征在于,在步骤S3中,挤出温度为150℃-180℃。
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