CN111875913A - 一种热风硅烷交联聚乙烯材料及其制备方法 - Google Patents
一种热风硅烷交联聚乙烯材料及其制备方法 Download PDFInfo
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Abstract
本发明公开了一种热风硅烷交联聚乙烯材料及其制备方法,该热风硅烷交联聚乙烯材料包括以下组分:线性低密度聚乙烯100份,复合稳定剂1~5份,复配硅烷0.8~3份;其中,所述复合稳定剂的组成为:100份线性低密度聚乙烯、0.5‑5份受阻酚类抗氧剂,0.1‑2份金属钝化剂,1‑10份氟化物加工助剂,0.1‑3份受阻聚剂;所述复配硅烷的组成为:180份乙烯基三甲氧基硅烷,6‑12份过氧化二异丙苯,3‑10份有机锡衍生物。该材料可在热风环境下完成交联过程,且交联所需时间较短,有效避免了温水或蒸汽交联导致的导体氧化等问题,而且成本低,效率高。
Description
技术领域
本发明属于高分子复合材料技术领域,具体涉及一种能在热风环境下交联的硅烷聚乙烯材料及其制备方法。
背景技术
传统“一步法硅烷温水交联聚乙烯”是通过分子结构由线性结构改变成3维网状结构,提高了线性低密度聚乙烯的耐热性由原来的70℃提高至90℃,也同时提高了机械性能及绝缘性能。因一步法硅烷温水交联聚乙烯价格低廉,使用简单,材料性能稳定,环保,作为电缆的绝缘体材料使用,在市场上使用得非常广泛,且逐步的在取代含毒性的聚氯乙烯材料。
一步法硅烷温水交联聚乙烯基础材料为线性低密度聚乙烯,通过添加入适量的硅烷,引发剂,催化剂及抗氧剂后经过单螺杆挤出机加温挤出,挤出胶体包覆在导体外层,经过冷却水槽定型后,便成为了电缆的绝缘体。
在电缆挤出绝缘后包裹在导体上,一般只是半成品,后续必需要在水温大约90℃的温水池或高温蒸气房里(温度在80℃以上)蒸煮约8-10个小时后才能完成分子从线性结构到网状结构的转变(也称为接枝交联或硫化)。因在水池或蒸汽房里存在压力,水容易进入导体层,导致导体氧化,氧化后的导体除表面发黑影响外观,同时也会增加了导体的电阻,直接导致导体的导电率降低。现有技术中也有只需要在室温下交联的研究,但是室温下交联通常需要比较长的反应时间。
发明内容
针对现有技术中的问题,本发明提供了一种热风硅烷交联聚乙烯材料,使需要在温水中或高温蒸汽房中完成的交联反应可以在热风环境下完成交联,且交联所需时间较短。
本发明所采用的技术方案具体如下:
一种热风硅烷交联聚乙烯材料,包括以下组分:
线性低密度聚乙烯 100份;
复合稳定剂 1~5份;
复配硅烷 0.8~3份;
其中,所述复合稳定剂的组成为:100份线性低密度聚乙烯、0.5-5份受阻酚类抗氧剂,0.1-2份金属钝化剂,1-10份氟化物加工助剂;
所述复配硅烷的组成为:180份乙烯基三甲氧基硅烷,6-12份过氧化二异丙苯,3-10份有机锡衍生物。
在上述技术方案中,所述受阻酚类抗氧剂为抗氧剂1010或/和抗氧剂1076;所述金属钝化剂为Irganox MD1024或/和Hostanox OSP 1;所述氟化物加工助剂为PPA2200、PPA2300、PPA2300MA和PPA2800中的一种或多种;
在上述技术方案中,所述有机锡衍生物为为单丁基三氯化锡和二丁基二氯化锡的混合物,所述单丁基三氯化锡与二丁基二氯化锡的质量比为1~2:1。
本发明另一方面提供了一种热风硅烷交联聚乙烯材料的制备方法,包括以下步骤:
S1、将100份线性低密度聚乙烯、0.5-5份受阻酚类抗氧剂、0.1-2份金属钝化剂和1-10份氟化物加工助剂按比例混合,经双螺杆挤出机造粒成复合稳定剂;
S2、将180份乙烯基三甲氧基硅烷,6-12份过氧化二异丙苯和3-10份有机锡衍生物按比例混合,得到复配硅烷;
S3、将线性低密度聚乙烯、复合稳定剂和复配硅烷按比例投入高速混合搅拌机充分混合,进入挤出机制成管材,经水槽冷却后,在热风下放置4~6小时,完成交联过程。
进一步地,在上述技术方案中,步骤S3所述的基础温度为:螺筒150~190℃,法兰温度200~230℃,口模温度220~240℃,转速为1000~1200转每分钟;所述热风的温度为60~70℃。
本发明的有益效果为:采用此配方组分的硅烷交联聚乙烯材料能够在挤出机内完成大部分的接枝,在进入水槽冷却时,绝缘体保留了一些水分,然后在60~70℃的热风下就能使聚合物大分子间交联,在较短的时间内就可以完成交联过程,避免了投入大量的资金建造温水交联池或蒸汽箱;另外采用热风完成接枝交联的过程中,还可以把制作电缆过程中以及冷却定型过程中引入的水分通过热风作用去除,有效避免了导体受潮。
具体实施方式
为了更好地理解本发明,以下通过具体实施例对本发明作进一步阐述,但并不作为对本发明的限定。
实施例1
热风硅烷交联聚乙烯材料,组分为(重量份):线性低密度聚乙烯100份,复合稳定剂3份,复配硅烷0.9份;其中,复合稳定剂的组成为:100份线性低密度聚乙烯、2份抗氧剂1010,0.5份Irganox MD1024,3份PPA2300MA;复配硅烷的组成为:180份乙烯基三甲氧基硅烷,10份过氧化二异丙苯,5份有机锡衍生物(单丁基三氯化锡与二丁基二氯化锡的质量比为2:1)。
制备过程如下:
将线性低密度聚乙烯、抗氧剂1010,Irganox MD1024,PPA2300MA按比例混合,经双螺杆挤出机造粒成复合稳定剂,所述挤出机的温度依次为1区:155℃,2区:155℃,3区160℃,4区:160℃,5区:165℃,6区:165℃,7区:170℃,8区:178℃,9区:185℃,10区:190℃,模头:195℃。
将乙烯基三甲氧基硅烷,过氧化二异丙苯和有机锡衍生物按比例混合,得到复配硅烷。
将线性低密度聚乙烯、复合稳定剂和复配硅烷按比例投入高速混合搅拌机充分混合,搅拌3分钟后取出用铝箔袋密封包装放置8小时。
将上步制备的混合料加入挤出机中,经挤出机制成电缆,挤出机的具体温度为:螺筒150~190℃,法兰温度210℃,口模温度230℃、挤出机的转速为1200转每分钟。挤出的产品经水槽冷却定型后,在热风装置中放置5小时,温度为70℃,完成交联过程。
对交联后的聚乙烯绝缘料进行以下检测,检测方法具体参照JB/T10437-2004,检测结果如下:
热延伸200℃,0.2Mpa,15分钟,负荷下伸长率变化率为70%,低于标准值(100%),说明交联度符合标准要求。冷却后永久变形率为0%,标准值为不大于5%。空气热老化前的拉伸强度为18.7Mpa,标准值为不小于13.5Mpa;空气热老化前的断裂伸长率为512%,标准值为不小于350%;空气热老化(135℃*168小时)后抗张强度变化率为+10%,标准值为±20%。断裂伸长率变化率为+5%,标准值为±20%。冲击脆化性能(-76℃)失效数为0/30个,标准值为失效数不超过15/30个。介质耗损因数(20℃,50Hz)为0.0005,标准值为不大于0.001。相对介电常数(20℃,50Hz)为2.12,标准值为不大于2.35。体积电阻率(20℃,1kV)为1*1015,标准值为不小于1*1014。介电强度为38MV/m标准值为不小于25MV/m,性能符合要求。
对由上述绝缘料制备的电缆进行检测,检测方法具体参照GB/T12706-2008,检测结果如下:
热延伸(200℃,0.2Mpa,15分钟),负荷下伸长率变化率为100%,低于标准值(175%),说明交联度符合标准要求。冷却后永久变形率为5%,标准值为不大于15%。空气热老化前的拉伸强度为21Mpa,标准值为不小于12.5Mpa;空气热老化前的断裂伸长率为430%,标准值为不小于200%;空气热老化(135℃,168小时),抗张强度变化率为+3%,标准值为±25%。断裂伸长率变化率为+1%,标准值为±25%。收缩实验(130℃,60分钟)为2%,标准值为不大于4%,性能符合要求。
实施例2
热风硅烷交联聚乙烯材料,组分为(重量份):线性低密度聚乙烯100份,复合稳定剂5份,复配硅烷2份;其中,复合稳定剂的组成为:100份线性低密度聚乙烯、5份抗氧剂,1份Hostanox OSP 1,7份PPA2200;复配硅烷的组成为:180份乙烯基三甲氧基硅烷,12份过氧化二异丙苯,10份有机锡衍生物(单丁基三氯化锡与二丁基二氯化锡的质量比为1.5:1)。
制备过程如下:
将线性低密度聚乙烯、抗氧剂1010,Hostanox OSP 1和PPA2200按比例混合,经双螺杆挤出机造粒成复合稳定剂,挤出机温度同实施例1。
将乙烯基三甲氧基硅烷,份过氧化二异丙苯和有机锡衍生物按比例混合,得到复配硅烷。
将线性低密度聚乙烯、复合稳定剂和复配硅烷按比例投入高速混合搅拌机充分混合,搅拌3分钟后取出用铝箔袋密封包装放置8小时。
在上步制备的混合料加入挤出机中,经进入挤出机制成电缆,挤出机的具体温度为:螺筒170℃~190℃,法兰温度210℃,口模温度230℃,挤出机的转速为1000转每分钟。挤出的电缆经水槽冷却定型后,在热风装置中放置4小时,温度为70℃,完成交联过程。
按照实施例1所述的检测方法进行检测,各项数据同样优于标准。
当然,以上仅是本发明的具体应用范例,对本发明的保护范围不构成任何限制。除上述实施例外,本发明还可以有其它实施方式。凡采用等同替换或等效变换形成的技术方案,均落在本发明所要求保护的范围之内。
Claims (7)
1.一种热风硅烷交联聚乙烯材料,其特征在于,包括以下组分:
线性低密度聚乙烯100份;
复合稳定剂1~5份
复配硅烷0.8~3份
其中,所述复合稳定剂的组成为:100份线性低密度聚乙烯、0.5-5份受阻酚类抗氧剂,0.1-2份金属钝化剂,1-10份氟化物加工助剂;
所述复配硅烷的组成为:180份乙烯基三甲氧基硅烷,6-12份过氧化二异丙苯,3-10份有机锡衍生物。
2.根据权利要求1所述的热风硅烷交联聚乙烯材料,其特征在于,所述受阻酚类抗氧剂为抗氧剂1010和抗氧剂1076中的一种或两种。
3.根据权利要求1所述的热风硅烷交联聚乙烯材料,其特征在于,所述金属钝化剂为Irganox MD1024或/和Hostanox OSP 1。
4.根据权利要求1所述的热风硅烷交联聚乙烯材料,其特征在于,所述氟化物加工助剂为PPA2200、PPA2300、PPA2300MA和PPA2800中的一种或多种。
5.根据权利要求1所述的热风硅烷交联聚乙烯材料,其特征在于,所述有机锡衍生物为单丁基三氯化锡和二丁基二氯化锡的混合物,所述单丁基三氯化锡与二丁基二氯化锡的质量比为1~2:1。
6.权利要求1~5任一权利要求所述热风硅烷交联聚乙烯材料的制备方法,其特征在于,包括以下步骤:
S1、将100份线性低密度聚乙烯、0.5-5份受阻酚类抗氧剂、0.1-2份金属钝化剂和1-10份氟化物加工助剂按比例混合,经双螺杆挤出机造粒成复合稳定剂;
S2、将180份乙烯基三甲氧基硅烷,6-12份过氧化二异丙苯和3-10份有机锡衍生物按比例混合,得到复配硅烷;
S3、将线性低密度聚乙烯、复合稳定剂和复配硅烷按比例投入高速混合搅拌机充分混合,进入挤出机制成管材,冷却后,在60~70℃热风下放置4~6小时,完成交联过程。
7.根据权利要求6所述的制备方法,其特征在于,步骤S3所述的挤出机温度为:螺筒150~190℃,法兰温度200~230℃,口模温度220~240℃,转速为1000~1200转每分钟。
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