CN112745558B - 一种高撕裂强度低烟无卤阻燃护套料及其制备方法和应用 - Google Patents
一种高撕裂强度低烟无卤阻燃护套料及其制备方法和应用 Download PDFInfo
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- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 title claims abstract description 24
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- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 claims abstract description 9
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Abstract
本发明提供了一种高撕裂强度低烟无卤阻燃电缆护套料及其制备方法和应用,所述护套料包括如下按重量份计算的组分:茂金属聚乙烯树脂25~45份;超高分子量聚乙烯5~15份;PE接枝马来酸酐3~8份;乙烯‑辛烯共聚物25~45份;乙烯‑醋酸乙烯酯共聚物10~30份;氢氧化铝90~125份;氢氧化镁30~60份;针状纳米填料4~9份;抗氧剂1~2份;润滑剂1~2份;所述针状纳米填料经过表面处理剂包覆处理。所述护套料的撕裂强度大于10N/mm;氧指数大于38;成品透光率大于等于70%。
Description
技术领域
本发明涉及电缆护套料技术领域,更具体地,涉及一种高撕裂强度高阻燃低烟无卤阻燃护套料及其制备方法和应用。
背景技术
电缆护套料为了满足低烟且无卤阻热的特性,往往是采用大量的氢氧化物阻燃剂填充,来满足标准要求的阻燃性能和烟密度性能。氢氧化物和树脂基体相容性较差,而低烟无卤阻燃护套料阻燃剂含量往往超过60%,因此材料的力学性能和撕裂强度会有比较大的下降,撕裂强度过低一般表现为护套料开裂,电缆护套开裂一般分为环向开裂和纵向开裂。
目前,国内还未有关于撕裂强度的要求,但是,随着科技的快速发展,对电缆护套料的要求也越来越高,急需开发一种高撕裂强度的护套料来满足要求。
中国专利(CN110294890A)公开了一种抗开裂阻燃电缆护套料及其制备方法,采用甲基乙烯基硅橡胶中的乙烯基与含氢硅油在氯铂酸的催化作用下形成交联的网状结构,使得护套料的力学性能和抗开裂性能好,但是从该专利的数据看,虽然采用热空气老化试验都没发生开裂,但是其撕裂强度并不高。
发明内容
本发明为克服上述现有技术所述的至少一种缺陷,提供一种高撕裂强度低烟无卤阻燃护套料。
本发明的另一目的在于提供所述高撕裂强度低烟无卤阻燃护套料的制备方法。
本发明的另一目的在于提供所述高撕裂强度低烟无卤阻燃护套料的应用。
为实现上述目的,本发明采用的技术方案是:
一种高撕裂强度低烟无卤阻燃电缆护套料,包括如下按重量份计算的组分:
所述针状纳米填料经过表面处理剂包覆处理。
本发明采用茂金属聚乙烯树脂和PE接枝马来酸酐、针状纳米填料共混,大大提高了树脂体系的撕裂强度;这是因为采用茂金属聚乙烯树脂和PE接枝马来酸酐共混后相容性更好,树脂支链更长,结晶度高,能够大幅度提高撕裂强度,而针状纳米填料因为其具有长径比,在共混体系中起到了增强的作用,也能提高撕裂强度;另外,针状纳米填料也可协效成炭,降低材料的烟密度。
优选地,所述茂金属聚乙烯树脂的共聚单体为1-己烯,所述茂金属聚乙烯树脂的密度为0.915~0.936g/cm3。
当茂金属聚乙烯树脂的的共聚单体为1-己烯时,其树脂的支链较多,能够提高树脂的撕裂强度,所述茂金属聚乙烯树脂的密度在0.915~0.936g/cm3,树脂结晶度更高,撕裂强度更好。
优选地,所述茂金属聚乙烯树脂在190℃,2.16kg条件下熔融指数小于等于3g/10min。熔融指数小于等于3g/10min时,撕裂强度更高。
超高分子量聚乙烯是指分子量大于等于100万的聚乙烯。
所述超高分子量聚乙烯的分子量为180~550万。
所述乙烯-醋酸乙烯酯共聚物在190℃,2.16kg条件下的熔融指数为0.5~3g/10min。
优选地,所述针状纳米填料为针状纳米碳酸钙和/或针状纳米硅灰石。
优选地,所述针状纳米填料的平均粒径为5~20nm;长径比为5~15。
优选地,所述PE接枝马来酸酐的共聚单体为1-己烯。
所述PE接枝马来酸酐的共聚单体为1-己烯时,其支链较长,抗撕裂强度更高,
优选地,所述PE接枝马来酸酐的马来酸酐接枝率大于等于0.8%。
所述PE接枝马来酸酐的马来酸酐接枝率的测定方法采用常规的方法即可,例如采用酸碱滴定法。
所述PE接枝马来酸酐重马来酸酐单体残留小于0.5‰。
所述氢氧化铝为经过表面处理的氢氧化铝,采用的表面处理剂为3-氨丙基三乙氧基硅烷,包覆率>99%。
所述氢氧化镁为经过表面处理的氢氧化镁,采用的表面处理剂为3-氨丙基三乙氧基硅烷,包覆率>99%。
所述抗氧剂为受阻酚类、受阻胺类、硫代酯类中的一种。
所述润滑剂为硬脂酸钙、聚乙烯蜡、硅油或硅酮母粒中一种。
本发明还提供所述高撕裂强度低烟无卤阻燃电缆护套料的制备方法,包括如下步骤:
S1.将线性低密度聚乙烯树脂、超高分子量聚乙烯和乙烯-辛烯共聚物按比例先通过双螺杆造粒、烘干。
S5.将步骤S1制备烘干的物料与PE接枝马来酸酐、乙烯-醋酸乙烯酯共聚物、氢氧化铝、氢氧化镁、针状纳米填料、抗氧剂和润滑剂按比例投入到密炼机中混炼、冷却、出料并进行造粒得到混合物。
所述双螺杆挤出机的长径比为48:1;所述双螺杆挤出机的温度为120~145℃。
所述密炼机的温度为145~160℃,密炼时间不低于10min。
所述高撕裂强度低烟无卤阻燃电缆护套料在制备电缆护套中的应用。
与现有技术相比,本发明的有益效果是:
本发明提供了一种高撕裂强度低烟无卤阻燃电缆护套料,采用茂金属聚乙烯树脂、PE接枝马来酸酐和针状纳米填料复配,能够大幅度提高树脂的撕裂强度,所述护套料的撕裂强度大于10N/mm;氧指数大于38;成品透光率大于等于70%。
具体实施方式
下面将对本发明实施例中的技术方案进行清楚、完整地描述,但本发明的实施方式不限于此。
本发明所采用的试剂、方法和设备,如无特殊说明,均为本技术领域常规试剂、方法和设备。
以下实施例及对比例中采用的原料如下:
茂金属聚乙烯树脂A1:熔指为2g/10min;共聚单体1-己烯;密度为0.918g/10cm3;市售
茂金属聚乙烯树脂B:熔指为2g/10min;共聚单体1-丁烯;密度为0.918g/10cm3;市售
茂金属聚乙烯树脂A2:熔指为2g/10min;共聚单体1-己烯;密度为0.92g/10cm3;市售
茂金属聚乙烯树脂A3:熔指为2g/10min;共聚单体1-己烯;密度为0.922g/10cm3;市售
茂金属聚乙烯树脂A4:熔指为2g/10min;共聚单体1-己烯;密度为0.925g/10cm3;市售
茂金属聚乙烯树脂A5:熔指为1g/10min;共聚单体1-己烯;密度为0.925g/10cm3;市售
茂金属聚乙烯树脂A6:熔指为3g/10min;共聚单体1-己烯;密度为0.925g/10cm3;市售
茂金属聚乙烯树脂A7:熔指为6g/10min;共聚单体1-己烯;密度为0.925g/10cm3;市售
聚乙烯树脂:SK化学牌号为FT810,熔指为2g/10min;密度为0.918,超高分子量聚乙烯树脂:分子量200万;牌号为泰科纳GUR 5113;
PE接枝马来酸酐A:共聚单体为1-己烯;接枝率0.8%,马来酸酐残留0.5‰;
PE接枝马来酸酐B:共聚单体为1-己烯;接枝率1.8%,马来酸酐残留0.5‰;
PE接枝马来酸酐C:共聚单体为1-己烯;接枝率3.5%,马来酸酐残留0.5‰;
PE接枝马来酸酐D:共聚单体为1-己烯;接枝率0.5%,马来酸酐残留0.5‰;
PE接枝马来酸酐的制备:选用基材为埃克森美孚公司牌号为Enable 1018茂金属PE,采用长径比为48:1双螺杆,采用侧喂料将引发剂和马来酸酐按比例喂料,双螺杆挤出机加工温度为120-160℃。
乙烯-辛烯共聚物:采用LG化学牌号LC 180,密度为0.891,熔指为1g/10min
乙烯-醋酸乙烯酯共聚物:埃克森美孚公司熔指为3g/10min;醋酸乙烯酯含量为28%
表面处理氢氧化铝:实验室自制;
表面处理氢氧化镁:实验室自制;
氢氧化铝/氢氧化镁包覆;氢氧化铝采用洛阳中超新材料股份有限公司牌号为AH-01DG氢氧化铝;氢氧化镁采用山东艾弗尔公司牌号为F5的氢氧化镁;在高混机中,将氢氧化铝/氢氧化镁加热到60℃,按比例加入3-氨丙基三乙氧基硅烷;高速混合30分钟。
针状纳米填料A1:针状纳米硅灰石;平均粒径为5nm;长径比为5
针状纳米填料A2:针状纳米硅灰石;平均粒径为10nm;长径比为5
针状纳米填料A3:针状纳米硅灰石;平均粒径为20nm;长径比为5
针状纳米填料A4:针状纳米硅灰石;平均粒径为30nm;长径比为5
针状纳米填料A5:针状纳米硅灰石;平均粒径为1nm;长径比为5
针状纳米填料A6:针状纳米硅灰石;平均粒径为10nm;长径比为10
针状纳米填料A7:针状纳米硅灰石;平均粒径为10nm;长径比为15
针状纳米填料A8:针状纳米硅灰石;平均粒径为10nm;长径比为20
针状纳米填料A9:针状纳米硅灰石;平均粒径为10nm;长径比为1
针状纳米填料A10:针状纳米碳酸钙;平均粒径为10nm;长径比为5
针状纳米填料A11:针状纳米碳酸钙和针状纳米碳酸钙1:1混合;平均粒径为10nm;长径比为5。
针状纳米碳酸钙制备:采用市售生石灰为原材料,Ca(OHO)2初始浓度为10-12%、碳化塔进口温度为45-75℃;添加复合结晶导向剂(由柠檬酸、H2SO4、EDTA组成),通入二氧化碳,当PH值6-7时停止通二氧化碳,反应液经过离心脱水、干燥、粉碎、筛分,得到针状纳米碳酸钙。
针状硅灰石制备:将硅灰石矿石先先用冲击粉碎机初步粉碎和富集;利用QS100型盘式气流粉碎机对初步粉碎的矿石进行细磨,改变给料压力,粉碎压力和给料速度,用不同目数的振动筛筛选得不同粒径和不同长径比的硅灰石。
其他填料:球形碳酸钙,桂林鑫龙矿业公司牌号为GXXL碳酸钙,
抗氧剂:采用抗氧剂1010和抗氧剂168组合,德国巴斯夫公司;
润滑剂:采用霍尼韦尔聚乙烯蜡AC-6A。
下面结合实施例来详细说明本发明。
下面实施例和对比例均通过以下方法制备光缆护套料,按照表1-3的重量比称取各组分;具体步骤如下:
S1.将线性低密度聚乙烯树脂、超高分子量聚乙烯和乙烯-辛烯共聚物按比例先通过双螺杆造粒、烘干。
S2.将步骤S1制备烘干的物料与PE接枝马来酸酐、乙烯-醋酸乙烯酯共聚物、氢氧化铝、氢氧化镁、针状纳米填料、抗氧剂和润滑剂按比例投入到密炼机中混炼、冷却、出料并进行造粒得到混合物。
所述双螺杆挤出机的长径比为48:1;所述双螺杆挤出机的温度为120~145℃。
所述密炼机的温度为145~160℃,密炼时间15min。
实施例1~6
表1实施例1~6的配方(份)
实施例1 | 实施例2 | 实施例3 | 实施例4 | 实施例5 | 实施例6 | |
茂金属聚乙烯树脂A1 | 35 | — | — | — | — | — |
茂金属聚乙烯树脂B | — | 35 | — | — | — | — |
茂金属聚乙烯树脂A2 | — | — | 35 | — | — | — |
茂金属聚乙烯树脂A3 | — | — | — | 35 | — | — |
茂金属聚乙烯树脂A4 | — | — | — | — | 35 | — |
茂金属聚乙烯树脂A5 | — | — | — | — | — | 35 |
超高分子量聚乙烯 | 10 | 10 | 10 | 10 | 10 | 10 |
PE接枝马来酸酐B | 5 | 5 | 5 | 5 | 5 | 5 |
乙烯-辛烯共聚物 | 40 | 40 | 40 | 40 | 40 | 40 |
乙烯醋酸乙烯酯共聚物 | 10 | 10 | 10 | 10 | 10 | 10 |
氢氧化铝 | 100 | 100 | 100 | 100 | 100 | 100 |
氢氧化镁 | 45 | 45 | 45 | 45 | 45 | 45 |
针状纳米填料A2 | 5 | 5 | 5 | 5 | 5 | 5 |
抗氧剂 | 1 | 1 | 1 | 1 | 1 | 1 |
润滑剂 | 1 | 1 | 1 | 1 | 1 | 1 |
实施例7~12
表2实施例7~12的配方(份)
实施例13~18
表3实施例13~18的配方(份)
实施例19~21和对比例1~5
表4实施例19~21和对比例1~5的配方(份)
将各实施例和对比例制备的粒料在平板硫化机上经180℃*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。电缆及电缆材料根据GB/T 32129-2015低烟无卤材料标准和GB 31247-2014B1阻燃等级标准的测试方法;撕裂强度根据GB/T529-2008方法测定。
表5实施例和对比例的数据
从实施例1~8看,茂金属PE的密度越高,熔指越低材料的撕裂强度、拉伸强度就越高。
从实施例9~11看,随着马来酸酐含量的增加,材料的裂强度、拉伸强度就越高。
从实施例12~21看,针状纳米填料的长径比越长材料的撕裂强度越高,针状纳米填料的粒径越小,材料的拉伸强度越高。
从对比例1~5看,采用非茂金属PE,撕裂强度和拉伸强度大幅度下降;采用普通填料,材料的撕裂强度也会大幅度下降。若不加入针状填料,其撕裂强度也会下降。若不加入相容剂,其茂金属聚乙烯树脂的相容性会很差,导致撕裂强度降低。
显然,本发明的上述实施例仅仅是为清楚地说明本发明所作的举例,而并非是对本发明的实施方式的限定。对于所属领域的普通技术人员来说,在上述说明的基础上还可以做出其它不同形式的变化或变动。这里无需也无法对所有的实施方式予以穷举。凡在本发明的精神和原则之内所作的任何修改、等同替换和改进等,均应包含在本发明权利要求的保护范围之内。
Claims (7)
2.根据权利要求1所述高撕裂强度低烟无卤阻燃电缆护套料,其特征在于,所述茂金属聚乙烯树脂在190℃,2.16kg条件下熔融指数为小于等于3g/10min。
3.根据权利要求1所述高撕裂强度低烟无卤阻燃电缆护套料,其特征在于,所述针状纳米填料为针状纳米碳酸钙和/或针状纳米硅灰石。
4.根据权利要求1所述高撕裂强度低烟无卤阻燃电缆护套料,其特征在于,所述PE接枝马来酸酐的共聚单体为1-己烯。
5.根据权利要求1所述高撕裂强度低烟无卤阻燃电缆护套料,其特征在于,所述PE接枝马来酸酐的接枝率大于等于0.8%。
6.根据权利要求1~5任一项所述高撕裂强度低烟无卤阻燃电缆护套料的制备方法,其特征在于,包括如下步骤:
S1.将线性低密度聚乙烯树脂、超高分子量聚乙烯和乙烯-辛烯共聚物按比例先通过双螺杆挤出机中造粒、烘干;
S2.将步骤S1制备烘干的物料与PE接枝马来酸酐、乙烯-醋酸乙烯酯共聚物、氢氧化铝、氢氧化镁、针状纳米填料、抗氧剂和润滑剂按比例投入到密炼机中混炼、冷却、出料并进行造粒得到混合物。
7.权利要求1~5任一项所述高撕裂强度低烟无卤阻燃电缆护套料在制备电缆护套中的应用。
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