CN111748051A - 一种乙烯-醋酸乙烯-硅烷三元共聚物及其制备方法 - Google Patents
一种乙烯-醋酸乙烯-硅烷三元共聚物及其制备方法 Download PDFInfo
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Abstract
本发明公开了一种乙烯‑醋酸乙烯‑硅烷三元共聚物及其制备方法，包括如下步骤：以50‑70％的乙烯气体、5.0％‑40％醋酸乙烯和0.5‑10％的硅烷为共聚单体，加入0‑10％分子量调节剂、0.09‑2.0％的引发剂，混合均匀；采用高压连续本体聚合法进行聚合反应，得到乙烯‑醋酸乙烯‑硅烷三元共聚物。本发明制备的硅烷共聚物：乙烯‑醋酸乙烯‑硅烷三元共聚物，其在电线电缆领域可替代硅烷接枝EVA或硅烷接枝PE，提高材料应用范围，与催化母料混合挤出温度控制范围较宽，不产生焦料，生产连续性好，稳定性高，同时可保证材料的交联度，也可作为低烟无卤高阻燃聚烯烃材料的基料树脂，提高阻燃剂的填充能力，改善交联程度及阻燃性能。
Description
技术领域
本发明涉及材料技术领域，具体涉及一种乙烯-醋酸乙烯-硅烷三元共聚物及其制备方法。
背景技术
随着电线电缆行业的不断发展以及人们环保意识的逐渐提高，人们越来越多地使用无卤阻燃电缆和硅烷交联电缆。由于EVA树脂具有良好的填料包容性和可交联性，因此在无卤阻燃电缆、半导体屏蔽电缆和二步法硅烷交联电缆中使用较多。另外，EVA树脂还被应用于制作一些特殊电缆的护套。EVA比PE的性能改善，主要是弹性、柔性、光泽性、透气性等方面，另外，它的耐环境应力开裂性得到了提高，对填料的受容性增大，可以采用加入较多增强填料的方法来避免或减少EVA力学性能比PE的下降。同时也可对EVA进行改性提升材料性能。
现有技术中，低烟无卤电缆料一般采用硅烷接枝树脂工艺，即先在树脂上接枝硅烷，硅烷水解形成硅醇，再缩合交联形成三维立体结构。但硅烷接枝物的使用仍存在一些问题，硅烷化合物接枝的聚合物制备存在的问题既有制备本身的问题也有关于制得材料性能的问题，接枝料的制备均为过氧化物引发接枝硅烷反应，反应温度较高，大多高于200℃，需设备温控高，另外过氧化物引入会引发部分树脂交联产生焦料，需定期停机清理设备中焦料等问题。同时，接枝料添加比例高虽可保证材料交联度，但却削弱了主料的优势，有预交联的风险，阻燃性能相对较低，而当硅烷接枝料添加少时虽可以保证接枝料基料的性能优势，能够改善材料的阻燃性能，但材料的交联程度就有不合格的风险。
发明内容
本发明要解决的技术问题是提供一种乙烯-醋酸乙烯-硅烷三元共聚物，生产过程中不产生焦料，生产连续性好，稳定性高，能耗低，能够不停机地连续生产，无需定期停机清理设备中焦料，制成的电缆料存储时间长，性能优异，也可作为低烟无卤阻燃聚烯烃电缆料的基料树脂，应用范围广。
本发明第一方面提供了一种乙烯-醋酸乙烯-硅烷三元共聚物的制备方法，包括如下步骤：以50-70％的乙烯气体、5.0％-40％醋酸乙烯和0.5-10％的硅烷为共聚单体，加入0-10％分子量调节剂、0.09-2.0％的引发剂，混合均匀；采用高压连续本体聚合法进行聚合反应，得到乙烯-醋酸乙烯-硅烷三元共聚物。
进一步地，所述的高压连续本体聚合法的反应条件为160-190℃，190-250MPa。
进一步地，所述的硅烷共聚单体为乙烯基三甲氧基硅烷、乙烯基三乙氧基硅烷、乙烯基三(β-甲氧基乙氧基)硅烷、乙烯基三乙酰氧基硅烷、乙烯基三丁酮肟基硅烷、γ-氨丙基三乙氧基硅烷、γ-缩水甘油醚氧丙基三甲氧基硅烷、γ-(甲基丙烯酰氧)丙基三甲氧基硅烷、γ-氯丙基三乙氧基硅烷、γ-氯丙基三甲氧基硅烷、3-氯丙基甲基二甲氧基硅烷中的一种或多种混合。
进一步地，所述的引发剂为过氧化苯甲酰、过氧化二异丙苯、过氧化苯甲酸叔丁酯中的一种或多种混合。
进一步地，所述的分子量调节剂为丙烷、丙烯、丙醛中的一种或多种混合。
进一步地，所述的高压连续本体聚合法具体包括如下步骤：
(1)工艺气体经过压缩后与乙烯气体、分子量调节剂汇合后压缩到20.0～28.5MPa后进入二次压缩机；
(2)将醋酸乙烯、硅烷注入二次压缩机机，以80～100℃的温度，200～240MPa的压力依次进入预冷器、深冷器、开车加热器、釜式反应器；
(3)将工艺气体以20～50℃的温度进入釜式反应器，并加入引发剂，在温度为160～190℃，压力190～250MPa下进行聚合反应。
进一步地，所述的高压连续本体聚合法还包括将生成的聚合物从反应釜底部排放，经过减压、降温、分离后，挤出、造粒、烘干得到所述的乙烯-醋酸乙烯-硅烷三元共聚物。
本发明的第二个目的是提供所述方法制备得到的乙烯-醋酸乙烯-硅烷三元共聚物。
本发明的第三个目的是提供所述的乙烯-醋酸乙烯-硅烷三元共聚物在制备低烟无卤阻燃聚烯烃电缆中的应用。
与现有技术相比，本发明的有益效果在于：
本发明制备的硅烷共聚物：乙烯-醋酸乙烯-硅烷三元共聚物，其在电线电缆领域可替代硅烷接枝EVA或硅烷接枝PE，提高材料应用范围，与催化母料混合挤出温度控制范围较宽，不产生焦料，生产连续性好，稳定性高，同时可保证材料的交联度，也可作为低烟无卤高阻燃聚烯烃材料的基料树脂，提高阻燃剂的填充能力，改善交联程度及阻燃性能。
具体实施方式
下面结合具体实施例对本发明作进一步说明，以使本领域的技术人员可以更好地理解本发明并能予以实施，但所举实施例不作为对本发明的限定。
除非另有定义，本文所使用的所有的技术和科学术语与属于本发明的技术领域的技术人员通常理解的含义相同。本文中在本发明的说明书中所使用的术语只是为了描述具体的实施例的目的，不是旨在于限制本发明。本文所使用的术语“及/或”包括一个或多个相关的所列项目的任意的和所有的组合。
实施例1
将600g乙烯、300g醋酸乙烯、80g乙烯基三甲氧基硅烷、10g丙烯分子量调节剂、8g过氧化苯甲酰引发剂采用高压连续本体聚合法制备EVA-乙烯基三乙氧基硅烷共聚物。
高压连续本体聚合法具体工艺：工艺气体经过压缩后与乙烯气体，分子量调节剂汇合进入初级压缩机，将气体压缩到20.0～28.5MPa进入二次压缩机。聚合单体醋酸乙烯、硅烷和高压循环系统返回来的工艺气体也注入二次机，以80～100℃的温度，200～240MPa的压力进入预冷器、深冷器、开车加热器。之后工艺气体以20～50℃的温度进入釜式反应器，此刻引发剂通过注入泵注入反应器，在温度为160～190℃，压力190～250MPa下进行聚合反应。生成的聚合物和部分工艺气体从反应釜底部排放后经过减压，降温，分离后，聚合物通过产品阀后挤出、造粒、烘干备用。
本实施例得到的EVA-乙烯基三乙氧基硅烷共聚物，产率达93％。
实施例2
1.取实施例1制备得到的乙烯-醋酸乙烯-硅烷共聚物60份、EVA树脂(牌号：2803)30份，相容剂(EVA-g-MAH)10份、阻燃剂(Mg(OH)2:Al(OH)3＝2:1)180份、分散剂(脂肪酸酰胺类)3份、抗氧剂(1010)1份和润滑剂(硬脂酸镁)0.5份，称重后，置于密炼机中混炼，混炼至料温为150℃时出料后，经双螺杆、单螺杆双阶挤出机挤出造粒，充分干燥后即得到共聚物阻燃料。
2.按照EVA树脂(牌号：2803)90份、相容剂(EVA-g-MAH)10份、催化剂(二月桂酸二丁基锡)2份、阻燃剂(Mg(OH)2:Al(OH)3＝2:1)160份，抗氧剂(1010)1份和润滑剂(硬脂酸镁)0.5份，称重后，置于密炼机中混炼，混炼至料温为140℃时出料后，经双螺杆、单螺杆双阶挤出机挤出造粒，充分干燥后即得到催化阻燃料。
3.按重量比90∶10的比例，将上述的共聚物阻燃料与催化阻燃料混合均匀，单螺杆挤制电线电缆，在80℃水浴浸没2h，即可达到交联效果。
实施例3
1.取实施例1制备得到的乙烯-醋酸乙烯-硅烷共聚物60份、EVA树脂(牌号：2803)20份，聚乙烯树脂(牌号：3364)8份，相容剂(EVA-g-MAH)12份、阻燃剂(Mg(OH)2:Al(OH)3＝2:1)170份、分散剂(脂肪酸酰胺类)3份、抗氧剂(1010)1份和润滑剂(硬脂酸镁)0.5份，称重后高置于速混合机中，在室温下搅拌5min，得到混合料，密炼机中混炼，混炼至料温为150℃时出料后，经单螺杆挤出机挤出造粒，充分干燥后即得到共聚物阻燃料。
2.按照EVA树脂(牌号：2803)80份、聚乙烯树脂(牌号：3364)8份，相容剂(EVA-g-MAH)12份、催化剂(二月桂酸二丁基锡)2份、阻燃剂(Mg(OH)2:Al(OH)3＝2:1)150份，抗氧剂(1010)1份和润滑剂(硬脂酸镁)0.5份，称重后高置于速混合机中，在室温下搅拌3～5min，得到混合料，密炼机中混炼，混炼至料温为150℃时出料后，经单螺杆挤出机挤出造粒，充分干燥后即得到催化阻燃料。
3.按重量比90∶10的比例，将上述的共聚物阻燃料与催化阻燃料混合均匀，单螺杆挤制电线电缆，在80℃水浴浸没2h，即可达到交联效果。
性能测试：
按照GB/T 1040.3、GB/T 18380.12、GB/T 18380.34规定的方法，对实施例2和3制备的电缆进行力学性能、耐候性和阻燃性测试，所得结果如下表所示：
上表的结果表明，本发明实施例2和3制备的电缆，在拉伸强度、断裂伸长率、耐空气热老化性能、阻燃性等多个指标上均符合要求。
以上所述实施例仅是为充分说明本发明而所举的较佳的实施例，本发明的保护范围不限于此。本技术领域的技术人员在本发明基础上所作的等同替代或变换，均在本发明的保护范围之内。本发明的保护范围以权利要求书为准。
Claims (10)
1.一种乙烯-醋酸乙烯-硅烷三元共聚物的制备方法，其特征在于，包括如下步骤：以50-70％的乙烯气体、5.0％-40％醋酸乙烯和0.5-10％的硅烷为共聚单体，加入0-10％分子量调节剂、0.09-2.0％的引发剂，混合均匀；采用高压连续本体聚合法进行聚合反应，得到乙烯-醋酸乙烯-硅烷三元共聚物。
2.根据权利要求1所述的制备方法，其特征在于，所述的高压连续本体聚合法的反应条件为160-190℃，190-250MPa。
3.根据权利要求1所述的制备方法，其特征在于，所述的硅烷共聚单体为乙烯基三甲氧基硅烷、乙烯基三乙氧基硅烷、乙烯基三(β-甲氧基乙氧基)硅烷、乙烯基三乙酰氧基硅烷、乙烯基三丁酮肟基硅烷、γ-氨丙基三乙氧基硅烷、γ-缩水甘油醚氧丙基三甲氧基硅烷、γ-(甲基丙烯酰氧)丙基三甲氧基硅烷、γ-氯丙基三乙氧基硅烷、γ-氯丙基三甲氧基硅烷、3-氯丙基甲基二甲氧基硅烷中的一种或多种混合。
4.根据权利要求1所述的制备方法，其特征在于，所述的引发剂为过氧化苯甲酰、过氧化二异丙苯、过氧化苯甲酸叔丁酯中的一种或多种混合。
5.根据权利要求1所述的制备方法，其特征在于，所述的分子量调节剂为丙烷、丙烯、丙醛中的一种或多种混合。
6.根据权利要求1所述的制备方法，其特征在于，所述的高压连续本体聚合法具体包括如下步骤：
(1)工艺气体经过压缩后与乙烯气体、分子量调节剂汇合后压缩到20.0～28.5MPa后进入二次压缩机；
(2)将醋酸乙烯、硅烷注入二次压缩机机，以80～100℃的温度，200～240MPa的压力依次进入预冷器、深冷器、开车加热器、釜式反应器；
(3)将工艺气体以20～50℃的温度进入釜式反应器，并加入引发剂，在温度为160～190℃，压力190～250MPa下进行聚合反应。
7.根据权利要求6所述的制备方法，其特征在于，所述的高压连续本体聚合法还包括将生成的聚合物从反应釜底部排放，经过减压、降温、分离后得到所述的乙烯-醋酸乙烯-硅烷三元共聚物。
8.根据权利要求7所述的制备方法，其特征在于，所述的乙烯-醋酸乙烯-硅烷三元共聚物还要经过挤出、造粒、烘干处理。
9.一种权利要求1～8任一项所述方法制备得到的乙烯-醋酸乙烯-硅烷三元共聚物。
10.权利要求9所述的乙烯-醋酸乙烯-硅烷三元共聚物在制备低烟无卤阻燃聚烯烃电缆中的应用。
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| JPS6210110A (ja) * | 1985-07-05 | 1987-01-19 | Mitsubishi Petrochem Co Ltd | 電気絶縁用エチレン共重合物架橋体 |
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