CN117247615A - 两步法硅烷自然交联热塑性弹性体电缆料及其制备方法 - Google Patents
两步法硅烷自然交联热塑性弹性体电缆料及其制备方法 Download PDFInfo
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Abstract
本发明中设计了两步法硅烷自然交联热塑性弹性体电缆料及其制备方法，本发明的方法硅烷自然交联热塑性弹性体电缆料是在现有的硅烷交联聚乙烯电缆材料的基础上，添加了苯乙烯类弹性体以及填充基础油，成为硅烷接支的苯乙烯弹性体材料，并和硅烷接支的聚乙烯一起水解交联成三维网络状结构，本发具有更优异的机械性能及更柔软的硬度。本发明的目的在于简化线缆生产工艺，不需要辐照和水煮交联，只需将生产的电线电缆存放在仓库内3～7天，或者在水中浸泡，或者在90℃温度下蒸汽蒸1h～5h就能达到交联合格，节省生产时间，降低线缆生产成本，并降低线缆硬度，提高材料的拉伸强度及伸长率，提高线缆的柔软性及弹性。
Description
技术领域
本发明属于电缆材料领域，特别是热塑性弹性体电缆料。
背景技术
一般聚烯烃的交联方式主要有三种：过氧化物交联、辐照交联和硅烷交联。目前电线电缆应用较多的是辐照交联聚烯烃电缆料，它是以聚乙烯为主要原料，加入交联剂、抗氧剂等助剂经混合、塑化、成粒而制得，然后经过高能电子束进行辐照交联。
制备电线电缆的顺序一般为：铜导体、绝缘材料挤出、护套材料挤出，绝缘材料挤出后需要送到辐照厂进行辐照，然后再进行护套挤出，再送到辐照厂进行辐照交联。在整个线缆制备过程中，第一，因两次往返辐照造成线缆厂运输成本较高；第二，交货时间周期较长，往往满足不了客户交期；第三，辐照交联聚烯烃线缆硬度高，施工不便。
发明内容
为解决上述技术问题，本发明方案提供了一种两步法硅烷自然交联热塑性弹性体电缆料，该电缆料用于电线电缆绝缘及护套，该电缆料由组合物A和组合物B混合组成，上述组合物A质量分数计为90-95份，上述组合物B质量分数计为5-10份，
上述组合物A以质量份数计包含以下组分：苯乙烯系弹性体：2-30份，低分子量填充剂：2-30份，聚烯烃弹性体：2-25份，聚乙烯树脂：5-35份，聚苯醚树脂：0-30份，阻燃剂：30-70份，抗氧剂：0-0.8份，硅烷：1.0-5.0份，过氧化物交联剂：0.1-5.0份；
上述组合物B以质量份数计包含以下组分：聚乙烯树脂：4.0-10.0份，有机锡催化剂：0.02-0.2份，抗氧剂：0-0.8份；
本发明还提供了一种两步法硅烷自然交联热塑性弹性体电缆料，其中，上述苯乙烯嵌段共聚物为丁二烯-苯乙烯共聚物SBS或氢化丁二烯-苯乙烯共聚物SEBS，上述苯乙烯含量为10%-60%以苯乙烯系弹性体的总重量计；上述聚烯烃弹性体为采用乙烯、丁烯或由乙烯、辛烯与一种或多种具有3-12碳原子的α-烯烃进行无规共聚而获得的物质，上述α-烯烃为丙烯、1-丁烯、1-己烯、1-辛烯、1-癸烯、1-十二烯等中的一种或多种并用；上述阻燃剂为氢氧化铝、氢氧化镁等无机阻燃剂但不限于这两种、三聚氰胺尿酸盐、次磷酸盐等磷氮类阻燃剂但不限于这两种中的一种或几种的任一比例混合。
上述硅烷为乙烯基三乙氧基硅烷、乙烯基三(β-甲氧乙氧基)硅烷、乙烯基三甲氧基硅烷中的一种或者几种但不限于枚举的这几种。
本发明还提供了一种两步法硅烷自然交联热塑性弹性体电缆料，上述过氧化物交联剂为过氧化二异丙苯、过氧化苯甲酰、二叔丁基过氧化物、过氧化氢二异丙苯中的一种或者几种但不限于枚举的这几种。
本发明还提供了一种两步法硅烷自然交联热塑性弹性体电缆料，上述有机锡催化剂为二丁基锡二月桂酸酯、辛酸亚锡、二(十二烷基硫)二丁基锡、二醋酸二丁基锡中的一种或者几种但不限于枚举的这几种。
本发明还提供了一种两步法硅烷自然交联热塑性弹性体电缆料，上述低分子量填充剂的运动粘度在40摄氏度时为6cSt-300cSt.
本发明还提供了一种两步法硅烷自然交联热塑性弹性体电缆料，上述聚苯醚树脂粉为淡黄色流动性粉状或颗粒状，上述聚苯醚树脂粉为25℃氯仿中测定的特性粘度在0.20dl/g-0.75dl/g之间的聚苯醚树脂。
本发明还提供了一种两步法硅烷自然交联热塑性弹性体电缆料，上述聚烯烃弹性体的熔融指数在0.5-5.0g/10min，以GB/T3682-2000法测定，测试条件为：温度为190℃，负荷为2.16KG。
本发明还提供了上述的一种两步法硅烷自然交联热塑性弹性体电缆料，上述聚乙烯树脂的熔融指数在0.5-5.0g/10min，以GB/T3682-2000法测定，测试条件为：温度为190℃，负荷为2.16KG。
本发明还提供了上述一种两步法硅烷自然交联热塑性弹性体电缆料的制备方法，包含以下步骤：将苯乙烯嵌段共聚物、增塑剂、聚苯醚树脂、聚烯烃弹性体、聚乙烯树脂、阻燃剂、抗氧剂、硅烷和过氧化物交联剂等全部材料或其中的重要组成部分先在混合设备中搅拌均匀，再经挤出机挤出，造粒，水分烘干然后包装，即成用于电线电缆绝缘和护套的两步法硅烷自然交联热塑性弹性体电缆料的组合物A。
本发明还提供了上述一种两步法硅烷自然交联热塑性弹性体电缆料，包含以下步骤：将聚乙烯树脂，有机锡催化剂，抗氧剂的所有组份或部分组份先在混合设备中搅拌均匀，再经挤出机挤出，造粒，水分烘干然后包装，即成用于电线电缆绝缘和护套的两步法硅烷自然交联热塑性弹性体电缆料的组合物B。
本发明还提供了上述一种两步法硅烷自然交联热塑性弹性体电缆料，包含以下步骤：使用A，B组分按比例混合均匀挤出线缆后，本发明的电缆料制备的电线电缆不用辐照，也不需要水煮，只需将生产的电线电缆存放在仓库内3～7天（时间长短取决于当时的空气湿度和温度），或者在90℃温度下蒸汽蒸1h～5h就能达到交联合格。
本发明制备的硅烷自然交联热塑性弹性体电缆料可以不用辐照，根据选用的交联催化剂，只需将生产的电线电缆存放在仓库内3～7天，靠空气中的湿度达到交联，或者在90℃温度下蒸汽蒸1h～5h就能达到交联合格。这样的工艺使得加工成本大幅降低，生产周期缩短，并且这样制得的材料比原来的材料的性能也有提高。
上述说明仅是本发明技术方案的概述，为了能够更清楚了解本发明的技术手段，并可依照说明书的内容予以实施，以下以本发明的较佳实施例详细说明如后。
具体实施方式
下面结合实施例，对本发明的具体实施方式作进一步详细描述。以下实施例用于说明本发明，但不用来限制本发明的范围。
实施了1
本发明公开了一种两步法硅烷自然交联热塑性弹性体电缆料，包括A料和B料。
上述A料包括以下组分：
| 序号 | 组分名称 | 组分含量 | 组分型号 | 来源 |
| 1 | 苯乙烯类嵌段共聚物弹性体 | 2-30 | 1651 | 科腾聚合物 |
| 2 | 填充基础油 | 2-30 | 150BS | 中国石油化工股份有限公司 |
| 3 | 聚烯烃弹性体 | 2-25 | 8480 | 陶氏化学 |
| 4 | 聚乙烯树脂 | 5-35 | 1802 | 扬子石化 |
| 5 | 聚苯醚树脂 | 0-30 | 040 | 蓝星化工新材料股份有限公司 |
| 6 | 阻燃剂 | 30-70 | 氢氧化铝 | 山东泰星新材料股份有限公司 |
| 7 | 抗氧剂 | 0-0.8 | B225 | 巴斯夫 |
| 8 | 硅烷 | 1.0-5.0 | A171 | 德国瓦克 |
| 9 | 过氧化物交联剂 | 0.1-5.0 | DCP | 上海方锐达化学品有限公司 |
上述B料包括以下组分：
| 序号 | 组分名称 | 组分含量 | 组分型号 | 来源 |
| 10 | 聚乙烯 | 4.0-10.0 | 1802 | 扬子石化 |
| 11 | 有机锡催化剂 | 0.02-0.2 | T12 | 美国空气化学 |
| 12 | 抗氧剂 | 0-0.8 | B225 | 巴斯夫 |
使用A，B组分按比例混合均匀挤出线缆后，本发明的电缆料制备的电线电缆不用辐照，也不需要水煮，只需将生产的电线电缆存放在仓库内3～7天（时间长短取决于当时的空气湿度和温度），或者在90℃温度下蒸汽蒸1h～5h就能达到交联合格。
实施例2
性能测试，测试方法见表内
注：以上物性为在90摄氏度90%相对湿度条件下存放3小时完成交联后测得的数据。
| 序号 | 优势效果 | 相关组分 | 测试方法 | 技术参数 | 对比参数 |
| 1 | 硬度低，更柔软 | 本发明混合物 | GB/T 531.1 | 82A | 87A |
| 2 | 拉伸弹性模量高 | 本发明混合物 | DIN EN ISO527-2:2012 | 21MPa | 12MPa |
| 3 | 拉伸强度高 | 本发明混合物 | GB/T528 | 15.0MPa | 11.0MPa |
| 4 | 断裂伸长率高 | 本发明混合物 | GB/T528 | 450% | 260% |
以上上述仅是本发明的优选实施方式，并不用于限制本发明，应当指出，对于本技术领域的普通技术人员来说，在不脱离本发明技术原理的前提下，还可以做出若干改进和变型，这些改进和变型也应视为本发明的保护范围。
Claims (10)
1.两步法硅烷自然交联热塑性弹性体电缆料，该电缆料由组合物A和组合物B混合组成，所述组合物A质量分数计为90-95份，所述组合物B质量分数计为5-10份；
所述组合物A以质量份数计包含以下组分：苯乙烯系弹性体：2-30份，填充基础油：2-30份，聚烯烃弹性体：2-25份，聚乙烯树脂：5-35份，聚苯醚树脂：0-30份，阻燃剂：30-70份，抗氧剂：0-0.8份，硅烷：1.0-5.0份，过氧化物交联剂：0.1-5.0份；
所述组合物B以质量份数计包含以下组分：聚乙烯树脂：4.0-10.0份，催化剂：0.02-0.2份，金属氧化物：0-0.5份，抗氧剂：0-0.8份。
2.根据权利要求1所述的两步法硅烷自然交联热塑性弹性体电缆料，其特征在于，所述苯乙烯嵌段共聚物为丁二烯-苯乙烯共聚物SBS或氢化丁二烯-苯乙烯共聚物SEBS，所述苯乙烯含量为10%-60%以苯乙烯系弹性体的总重量计；所述聚烯烃弹性体为采用乙烯、丁烯或由乙烯、辛烯与一种或多种具有3-12碳原子的α-烯烃进行无规共聚而获得的物质，所述α-烯烃为丙烯、1-丁烯、1-己烯、1-辛烯、1-癸烯、1-十二烯等中的一种或多种并用；所述阻燃剂为氢氧化铝、氢氧化镁等无机阻燃剂但不限于这两种、三聚氰胺尿酸盐、次磷酸盐等磷氮类阻燃剂但不限于这两种中的一种或几种的任一比例混合；
所述硅烷为乙烯基三乙氧基硅烷、乙烯基三(β-甲氧乙氧基)硅烷、乙烯基三甲氧基硅烷中的一种或者几种。
3.根据权利要求2所述的两步法硅烷自然交联热塑性弹性体电缆料，其特征在于，所述过氧化物交联剂为过氧化二异丙苯、过氧化苯甲酰、二叔丁基过氧化物、过氧化氢二异丙苯，叔丁基过氧化3，5，5-三甲基乙酯等过氧化酯类中的一种或者几种。
4.根据权利要求2所述的两步法硅烷自然交联热塑性弹性体电缆料，其特征在于，所述催化剂为二丁基锡二月桂酸酯、辛酸亚锡、二(十二烷基硫)二丁基锡、二醋酸二丁基锡，十二烷基苯磺酸（K12），十二烷基苯磺化乙酰，甲苯磺酸，甲苯硫化乙酰，甲磺化乙酰，萘磺酸，四丙基苯磺酸中的一种或者几种，或者由过氧化酯与金属氧化物反应生成的盐类。
5.根据权利要求2所述的两步法硅烷自然交联热塑性弹性体电缆料，其特征在于，所述填充基础油的运动粘度在40摄氏度时为6cSt-300cSt。
6.根据权利要求2所述的两步法硅烷自然交联热塑性弹性体电缆料，其特征在于，所述聚苯醚树脂粉为淡黄色流动性粉状或颗粒状，所述聚苯醚树脂粉为25℃氯仿中测定的特性粘度在0.20dl/g-0.75dl/g之间的聚苯醚树脂。
7.根据权利要求2所述的两步法硅烷自然交联热塑性弹性体电缆料，其特征在于，所述聚烯烃弹性体的熔融指数在0.5-5.0g/10min。
8.根据权利要求2所述的两步法硅烷自然交联热塑性弹性体电缆料，其特征在于，所述聚乙烯树脂的熔融指数在0.5-5.0g/10min。
9.权利要求1至8所述的任意一种两步法硅烷自然交联热塑性弹性体电缆料的制备方法，其特征在于，所述方法包含以下步骤：将苯乙烯嵌段共聚物、基础油、聚苯醚树脂、聚烯烃弹性体、聚乙烯树脂、阻燃剂、抗氧剂、硅烷和过氧化物引发剂等全部材料或其中的重要组成部分先在混合设备中搅拌均匀，再经挤出机挤出，造粒，水分烘干然后包装，即成用于电线电缆绝缘和护套的两步法硅烷自然交联热塑性弹性体电缆料的组合物A，
所述方法包含以下步骤：将聚乙烯树脂，交联催化剂，金属氧化物，抗氧剂的所有组份或部分组份先在混合设备中搅拌均匀，再经挤出机挤出，造粒，水分烘干然后包装，即成用于电线电缆绝缘和护套的两步法硅烷自然交联热塑性弹性体电缆料的组合物B。
10.根据权利要求9所述的两步法硅烷自然交联热塑性弹性体电缆料的制备方法，其特征在于，所述方法还包括使用A，B组分按比例混合均匀挤出线缆后，将生产的电线电缆存放在仓库内3～7天或者在90℃温度下蒸汽蒸1h～5h。
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