CN106188815B - 耐高温老化的交联乙烯-四氟乙烯共聚物材料 - Google Patents

耐高温老化的交联乙烯-四氟乙烯共聚物材料 Download PDF

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CN106188815B
CN106188815B CN201610596142.8A CN201610596142A CN106188815B CN 106188815 B CN106188815 B CN 106188815B CN 201610596142 A CN201610596142 A CN 201610596142A CN 106188815 B CN106188815 B CN 106188815B
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史丛丛
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Cgnpc Delta (jiangsu) Plastic Co Ltd
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Abstract

本发明一种耐高温老化的交联乙烯‑四氟乙烯共聚物材料，由以下质量份的组分组成：乙烯‑四氟乙烯共聚物、预聚物交联剂、N，N’‑双[β‑(3，5‑二叔丁基‑4‑羟基苯基)丙酰]肼、1,3,5‑三(3,5‑二叔丁基‑4‑羟基苄基)异氰尿酸、三氧化二锑、五氧化二锑、N,N'‑乙撑双硬脂酰胺、季戊四醇硬脂酸酯、白油；预聚物交联剂的重均分子量为600~3000，1,3,5‑三(3,5‑二叔丁基‑4‑羟基苄基)异氰尿酸与N，N’‑双[β‑(3，5‑二叔丁基‑4‑羟基苯基)丙酰]肼的重量份比例为3：0.9~1.2；1,3,5‑三(3,5‑二叔丁基‑4‑羟基苄基)异氰尿酸与N，N’‑双[β‑(3，5‑二叔丁基‑4‑羟基苯基)丙酰]肼的重量份比例为3：1。本发明稳定性非常好，加工的成品颜色非常白，经辐照后也不变色。

Description

耐高温老化的交联乙烯-四氟乙烯共聚物材料
技术领域
本发明涉及特种电线电缆材料，尤其涉及辐照交联乙烯-四氟乙烯共聚绝缘料。
背景技术
乙烯-四氟乙烯共聚物（ETFE）又称F40，透明结晶料，熔点为265～280℃，是最强韧和最轻的氟塑料。ETFE具有优良的介电性、绝缘性能和力学性能，耐辐照，耐开裂，耐老化，耐各种化学溶剂，耐高低温，长期工作温度在-65℃到150℃之间。ETFE树脂经辐照交联后，耐辐射性能，抗拉强度和抗老化性能大大提升，长期工作温度提高到200℃，被大量用于特种电缆绝缘料，如运输、航空、化学和核工厂、油井以及井下的各种线缆和通讯线的绝缘。辐照交联乙烯-四氟乙烯（XETFE）绝缘电线电缆是目前飞机安装线两大主要线种之一。目前X-ETFE绝缘料的技术掌握在国外少数几家著名的电线电缆生产厂家中，价格昂贵，供货周期长，遇到特殊时期对我国实行销售管控。目前的XETFE绝缘料生产过程中发烟量大，污染环境；交联剂易自聚，且对加工温度的要求苛刻，在加工过程中热稳定性差，易发黄，且辐照后颜色加深。因此如何克服上述技术问题，成为本领域技术人员努力的方向。
发明内容
本发明的目的是提供一种耐高温老化的交联乙烯-四氟乙烯共聚物材料，该耐高温老化的交联乙烯-四氟乙烯共聚物材料解决目前的XETFE绝缘料加工过程中发烟量高、交联剂易自聚、对加工温度要求较为苛刻的问题，填补国内空白；且本发明生产的电缆料经高温老化后，产品拉伸强度和断裂伸长率的保留率高，本发明所述的预聚物交联剂更适合高温使用的交联电缆料。
为达到上述发明目的，本发明采用的技术方案是：一种耐高温老化的交联乙烯-四氟乙烯共聚物材料，由以下质量份的组分组成：
乙烯-四氟乙烯共聚物（ETFE） 100份，
预聚物交联剂 0.3~8份，
N，N’-双[β- (3，5-二叔丁基-4-羟基苯基)丙酰]肼 0.1~1份，
1,3,5-三(3,5-二叔丁基-4-羟基苄基)异氰尿酸 0.5~3份，
三氧化二锑 1~5份，
五氧化二锑 1~3份，
N,N'-乙撑双硬脂酰胺 0.1~2份
季戊四醇硬脂酸酯 0.1~0.5份，
白油 0.1~3份；
所述预聚物交联剂化学结构式如下：
其中X为乙烯基、烯丙基、甲代烯丙基、炔丙基或以上几种的组合，n= 2~15；
所述预聚物交联剂的重均分子量为600~3000，所述1,3,5-三(3,5-二叔丁基-4-羟基苄基)异氰尿酸与N，N’-双[β- (3，5-二叔丁基-4-羟基苯基)丙酰]肼的重量份比例为3：0.9~1.2；
所述1,3,5-三(3,5-二叔丁基-4-羟基苄基)异氰尿酸与N，N’-双[β- (3，5-二叔丁基-4-羟基苯基)丙酰]肼的重量份比例为3：1。
上述技术方案进一步改进的技术方案如下：
1. 上述方案中，所述X为甲代烯丙基。
2. 上述方案中，所述1,3,5-三(3,5-二叔丁基-4-羟基苄基)异氰尿酸与N，N’-双[β- (3，5-二叔丁基-4-羟基苯基)丙酰]肼的重量份比例为3：1。
3. 上述方案中，所述预聚物交联剂的重均分子量为600~5000。
由于上述技术方案的运用，本发明与现有技术相比具有下列优点：
1. 本发明的耐高温老化的交联乙烯-四氟乙烯共聚物材料加工过程中发烟量低，还有一种非常好的性能，就是加工过程中预聚物交联剂热稳定性非常好，加工的成品颜色非常白，经辐照后也不变色；而用单体交联剂的产品，加工过程中发烟量非常大，交联剂不稳定，产品易发黄，辐照后颜色加深。
2. 本发明的耐高温老化的交联乙烯-四氟乙烯共聚物材料，其经高温老化后，所测拉伸强度和断裂伸长率的保留率，相对现有的采用单体交联剂的产品的拉伸强度和断裂伸长率保留率高，本发明所述的预聚物交联剂更适合高温使用的交联电缆料。
3. 本发明的耐高温老化的交联乙烯-四氟乙烯共聚物材料，1,3,5-三(3,5-二叔丁基-4-羟基苄基)异氰尿酸与N，N’-双[β- (3，5-二叔丁基-4-羟基苯基)丙酰]肼共同使用，比单独加入其中任何一种，抗氧效果都好。其中1,3,5-三(3,5-二叔丁基-4-羟基苄基)异氰尿酸与N，N’-双[β- (3，5-二叔丁基-4-羟基苯基)丙酰]肼的重量份比例为3：1协同作用抗氧效果最好。具体测试方法： 将加入不同种类和含量抗氧剂的绝缘料，压片（1mm），辐照交联后经250℃（辐照剂量12M），7h老化，观察外表颜色变化，结果见表1。三氧化二锑用于含氟的乙烯-四氟乙烯有很好的阻燃效果，并且可用于HF吸收剂，以防止HF浓度过大影响辐照过程中的交联效果，并提高电线的使用寿命。
具体实施方式
下面结合实施例对本发明作进一步描述：
实施例1~3：一种耐高温老化的交联乙烯-四氟乙烯共聚物材料，由以下质量份的组分组成：
乙烯-四氟乙烯共聚物 100份，
预聚物交联剂 0.3~8份，
N，N’-双[β- (3，5-二叔丁基-4-羟基苯基)丙酰]肼 0.1~1份，
1,3,5-三(3,5-二叔丁基-4-羟基苄基)异氰尿酸 0.5~3份，
三氧化二锑 1~5份，
五氧化二锑 1~3份，
N,N’-乙撑双硬脂酰胺 0.1~2份
季戊四醇硬脂酸酯 0.1~0.5份，
白油 0.1~3份；
所述预聚物交联剂化学结构式如下：
其中X为乙烯基、烯丙基、甲代烯丙基、炔丙基或以上几种的组合，n= 2~15；
所述预聚物交联剂的重均分子量为600~3000，所述1,3,5-三(3,5-二叔丁基-4-羟基苄基)异氰尿酸与N，N’-双[β- (3，5-二叔丁基-4-羟基苯基)丙酰]肼的重量份比例为3：0.9~1.2。
优选预聚物交联剂的重均分子量为1000~3000。
表1 抗氧剂种类对产品抗氧化性能的影响
所述耐高温老化的交联乙烯-四氟乙烯共聚物材料具体由以下重量份组分组成，如表2所示：
表2
一种用于上述耐高温老化的交联乙烯-四氟乙烯共聚物材料的制备方法，包括以下步骤：
第一步：将按配方重量计量的乙烯-四氟乙烯共聚物100份、N，N’-双[β- (3，5-二叔丁基-4-羟基苯基)丙酰]肼0.1~1份、1,3,5-三(3,5-二叔丁基-4-羟基苄基)异氰尿酸0.5~3份、三氧化二锑1~5份、五氧化二锑1~3份、预聚物交联剂0.3~8份、N,N'-乙撑双硬脂酰胺（EBS）0.1~2份、季戊四醇硬脂酸酯（PETS）0.1~0.5份、白油在高速混合机中均匀混合10min后取出；
第二步：将混合均匀的原料在加料口加入，在双螺杆挤出机中挤出造粒，熔融挤出温度为240~340℃；然后烘干并包装，获得耐高温老化的交联乙烯-四氟乙烯共聚物材料。
将所得电缆料经压片，辐照后，经300℃，7h老化，然后取出，室温冷却24h，测其拉伸强度和断裂伸长率保留率，与用TMAIC做交联剂的样品做对比。测试方法：GJB-773A2000, （50±5）mm/min，结果如表3。
表3
从表3中性能可以看出，采用本发明耐高温老化的交联乙烯-四氟乙烯共聚物材料，其测拉伸强度和断裂伸长率的保留率，相对于用单体交联剂的产品的拉伸强度和断裂伸长率的保留率高。其次，加工过程中发烟量低，还有一种非常好的性能，就是加工过程中预聚物交联剂热稳定性非常好，加工的成品颜色非常白，经辐照后也不变色，而用单体交联剂的产品，加工过程中，交联剂不稳定，产品易发黄，辐照后颜色加深。
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 (1)

1.一种耐高温老化的交联乙烯-四氟乙烯共聚物材料，其特征在于：由以下质量份的组分组成：
乙烯-四氟乙烯共聚物（ETFE） 100份，
预聚物交联剂 0.3~8份，
N，N’-双[β- (3，5-二叔丁基-4-羟基苯基)丙酰]肼 0.1~1份，
1,3,5-三(3,5-二叔丁基-4-羟基苄基)异氰尿酸 0.3~3份，
三氧化二锑 1~5份，
五氧化二锑 1~3份，
N,N'-乙撑双硬脂酰胺 0.1~2份
季戊四醇硬脂酸酯 0.1~0.5份，
白油 0.1~3份；
所述预聚物交联剂化学结构式如下：
；
其中X为甲代烯丙基，n= 2~15；
所述预聚物交联剂的重均分子量为600~5000，所述1,3,5-三(3,5-二叔丁基-4-羟基苄基)异氰尿酸与N，N’-双[β- (3，5-二叔丁基-4-羟基苯基)丙酰]肼的重量份比例为3：1。
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