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CN108359131B - 用于白色电线电缆pvc胶料的钙锌复合稳定剂 - Google Patents

用于白色电线电缆pvc胶料的钙锌复合稳定剂 Download PDF

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CN108359131B
CN108359131B CN201810258285.7A CN201810258285A CN108359131B CN 108359131 B CN108359131 B CN 108359131B CN 201810258285 A CN201810258285 A CN 201810258285A CN 108359131 B CN108359131 B CN 108359131B
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罗志强
陈朗秋
刘敏娜
邓克
刘奇志
吴婕妤
罗炜艳
倪娴娴
孙超华
雷雅钦
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Xiangtan University
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Abstract

本发明涉及一种用于白色电线电缆PVC胶料的钙锌复合稳定剂的制备方法，其由下列原料制备而成：硬脂酸钙、硬脂酸锌、三羟乙基异氰尿酸酯（赛克）、抗氧剂1,3,5‑三(3,5‑二叔丁基‑4‑羟基苯基丙酰氧基乙基)异氰尿酸酯（抗氧剂3125）、抗氧剂硫代二丙酸二硬脂醇酯（DSTP）或硫代二丙酸双月桂酯（DLTP）、二乙基次膦酸铝、硬脂酰苯甲酰甲烷、水滑石。这种白色电线电缆PVC胶料的钙锌复合稳定剂无毒环境友好，对PVC胶料具有好的热稳定作用和着色抑制力。

Description

用于白色电线电缆PVC胶料的钙锌复合稳定剂
技术领域
本发明涉及一种用于白色电线电缆PVC胶料的钙锌复合稳定剂。
背景技术
在电线电缆行业中，聚氯乙烯（PVC）材料因制造成本低、力学性能优良、具有良好加工性能，耐腐蚀，绝缘等特点，得到广泛使用，如电线电缆绝缘层和护套。
然而聚氯乙烯（PVC）是分子链中含有诸多氯原子的高分子聚合物，由于氯原子和整个分子链中电子云分布的明显不均匀性，使分子链出现了严重的缺陷。因此PVC在加工和使用过程中，收到热、机械剪切力、氧气和光的影响，很容易降解受到破坏，其前期降解的表现就是变色，最终还会影响到PVC产品的外观和使用寿命。在电线电缆胶粒制造过程中，聚氯乙烯（PVC）生产胶料的稳定性是影响电线电缆产品性能的关键；特别是白色的电线电缆，其对电线电缆的白度及不变色的要求较高；因此对用于白色电线电缆胶料PVC材料的加工过程所使用的稳定剂有较高要求。
发明内容
本发明的目的是针对白色电线电缆聚氯乙烯（PVC）胶料的生产和质量要求，提供一种用于白色电线电缆PVC胶料的钙锌复合稳定剂。
为了解决上述问题，本发明采用的技术方案如下：
用于白色电线电缆PVC胶料的钙锌复合稳定剂，由下列原料制备而成：硬脂酸钙 、硬脂酸锌 、三羟乙基异氰尿酸酯 （赛克）、抗氧剂1,3,5-三(3,5-二叔丁基-4-羟基苯基丙酰氧基乙基)异氰尿酸酯（抗氧剂3125）、抗氧剂硫代二丙酸二硬脂醇酯（DSTP）或硫代二丙酸双月桂酯（DLTP）、二乙基次膦酸铝、硬脂酰苯甲酰甲烷、水滑石 。
用于白色电线电缆PVC胶料的钙锌复合稳定剂中各组分的份量为：硬脂酸钙 300-400Kg、硬脂酸锌 100-140Kg、三羟乙基异氰尿酸酯 （赛克）50-78Kg、抗氧剂1,3,5-三(3,5-二叔丁基-4-羟基苯基丙酰氧基乙基)异氰尿酸酯（抗氧剂3125） 15-20Kg、抗氧剂硫代二丙酸二硬脂醇酯（DSTP）或硫代二丙酸双月桂酯（DLTP）15-30Kg、二乙基次膦酸铝8-15Kg、硬脂酰苯甲酰甲烷12-20Kg、水滑石 60-120Kg。
聚氯乙烯PVC钙锌复合稳定剂普遍使用的抗氧剂是抗氧剂 β-（3,5-二叔丁基-4-羟基苯基）丙酸正十八碳醇酯(抗氧剂1076)、抗氧剂四[β-（3，5-二叔丁基-4-羟基苯基）丙酸]季戊四醇酯（抗氧剂1010）、抗氧剂亚磷酸三(2,4-二叔丁基苯基)酯(抗氧剂168)等。例如CN106366514A。
三羟乙基异氰尿酸酯 （赛克）作为一种高效辅助稳定剂已经广泛使用，例如US5938977；但其与含相似分子骨架的抗氧剂1,3,5-三(3,5-二叔丁基-4-羟基苯基丙酰氧基乙基)异氰尿酸酯（抗氧剂3125）协同使用，并配合硫醚抗氧剂硫代二丙酸二硬脂醇酯（DSTP）或硫代二丙酸双月桂酯（DLTP）、二乙基次膦酸铝是本发明所提出方案。
具体实施方式
下面结合实施例对本发明做进一步详细说明；
下面的实施例是对本发明的解释，本发明的保护范围不受以下实施例局限。
实施例 采用以下原料制备用于白色电线电缆PVC胶料的钙锌复合稳定剂。
（1）按以下配方称取各原料：硬脂酸钙 360Kg、硬脂酸锌 120Kg、三羟乙基异氰尿酸酯 （赛克）50Kg、抗氧剂1,3,5-三(3,5-二叔丁基-4-羟基苯基丙酰氧基乙基)异氰尿酸酯（抗氧剂3125） 15Kg、抗氧剂硫代二丙酸二硬脂醇酯（DSTP）或硫代二丙酸双月桂酯（DLTP）18Kg、二乙基次膦酸铝10Kg、硬脂酰苯甲酰甲烷12Kg、水滑石 100Kg。
（2）将上述原料经混合、粉碎、过筛、装包，得到用于白色电线电缆PVC胶料的钙锌复合稳定剂。
对比例 采用以下原料制备用于对比的电线电缆PVC胶料钙锌复合稳定剂。
（1）按以下配方称取各原料：硬脂酸钙 360Kg、硬脂酸锌 120Kg、三羟乙基异氰尿酸酯 （赛克）50Kg、抗氧剂 β-（3,5-二叔丁基-4-羟基苯基）丙酸正十八碳醇酯(抗氧剂1076) 15Kg、抗氧剂亚磷酸三(2,4-二叔丁基苯基)酯(抗氧剂168)18Kg、硬脂酰苯甲酰甲烷12Kg、水滑石 100Kg。
（2）将上述原料经混合、粉碎、过筛、装包，得到对比用电线电缆PVC胶料钙锌复合稳定剂。
白色电线电缆PVC胶料的钙锌复合稳定剂性能对比测试实验。
刚果红实验（PVC静态热稳定性）
将试样维持在材料规定的测试温度，测定导致刚果红试纸变蓝所经过的时间，即为稳定时间，按照GB/T2917.1-2002测试，控制油浴温度为180±1℃。
将实施例或对比例配制的稳定剂按如下配方：
PVC ：100份、重质碳酸钙：40份、增塑剂DOP：35份、氯化石蜡：15份、
实施例制得的稳定剂：5份，或对比例制得的稳定剂：5份，将各组分混合均匀。
然后将混合物料于180℃，在双辊筒炼胶机上混炼5min。对所得PVC料进行刚果红时间测试。
实验测得：对比例制得的稳定剂所得PVC料刚果红时间为65min。
实施例制得的稳定剂所得PVC料刚果红时间为116min。
实验结果表明，实施例制得的稳定剂的热稳定性能好。
试片耐热性能测试（PVC试片烘变色时间）
将实施例制得的稳定剂，或对比例制得的稳定剂按如下配方混合：
PVC 100份、重质碳酸钙 40份、增塑剂DOP 35份、氯化石蜡 15份
实施例制得的稳定剂：5份，或对比例制得的稳定剂：5份，将各组分混合均匀。
然后将混合物料在双辊筒炼胶机上混炼5min，辊筒温度180℃，拉下厚度为0.3mm的样片，取片后剪成2cm×2cm小方块试样，制取试片组，进行实验：将制取的试片组放入老化试验箱中进行180℃下热稳定性测试。每隔10 min取出一个试片，比较各试片颜色变化情况。
试片耐热性实验结果如下：
时间/min 10 20 30 40 50 60
对比例稳定剂试片 白色 白色 白色 白色 浅黄 浅橙
实施例稳定剂试片 白色 白色 白色 白色 白色 白色
时间/min 70 80 90 100 110 120 130
对比例稳定剂试片 棕色 黑色
实施例稳定剂试片 白色 白色 白色 浅黄 浅橙 棕色 黑色
实验结果表明，实施例制得的稳定剂有较好的热稳定性能及较强着色抑制力。

Claims (2)

1.一种用于白色电线电缆PVC胶料的钙锌复合稳定剂，其特征在于：它是由下列的原料制备而成：硬脂酸钙、硬脂酸锌、三羟乙基异氰尿酸酯、抗氧剂1,3,5-三(3,5-二叔丁基-4-羟基苯基丙酰氧基乙基)异氰尿酸酯、抗氧剂硫代二丙酸二硬脂醇酯或抗氧剂硫代二丙酸双月桂酯、二乙基次膦酸铝、硬脂酰苯甲酰甲烷、水滑石。
2.根据权利要求1所述用于白色电线电缆PVC胶料的钙锌复合稳定剂，其中各组分的份量为：硬脂酸钙 300-400Kg、硬脂酸锌 100-140Kg、三羟乙基异氰尿酸酯50-78Kg、抗氧剂1,3,5-三(3,5-二叔丁基-4-羟基苯基丙酰氧基乙基)异氰尿酸酯15-20Kg、抗氧剂硫代二丙酸二硬脂醇酯或硫代二丙酸双月桂酯15-30Kg、二乙基次膦酸铝8-15Kg、硬脂酰苯甲酰甲烷12-20Kg、水滑石 60-120Kg。
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