CN103819807A - 辐射交联的聚烯烃弹性体膜及其制备方法 - Google Patents

辐射交联的聚烯烃弹性体膜及其制备方法 Download PDF

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CN103819807A
CN103819807A CN201410061030.3A CN201410061030A CN103819807A CN 103819807 A CN103819807 A CN 103819807A CN 201410061030 A CN201410061030 A CN 201410061030A CN 103819807 A CN103819807 A CN 103819807A
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polyolefin elastomer
elastomer film
radiation crosslinking
film
radiation
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CN103819807B (zh
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李民
王权
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SHANGHAI HIUV ELECTRONIC TECHNOLOGY Co Ltd
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Abstract

本发明公开了一种辐射交联的聚烯烃弹性体膜，包括以下重量份的组分：聚烯烃弹性体69～99.8份，助交联剂0.01～5份，抗氧剂0.01～2份，硅烷偶联剂0～2份，有机过氧化物交联剂0～2份，颜料0～20份。本发明还公开了一种上述辐射交联的聚烯烃弹性体膜的制备方法：将聚烯烃弹性体69～99.8份，助交联剂0.01～5份，抗氧剂0.01～2份，硅烷偶联剂0～2份，有机过氧化物交联剂0～2份和颜料0～20份，充分混合后加入挤出机，通过T形平板模具挤出成膜，经过辐射交联的方法得到辐射交联的聚烯烃弹性体膜。由于在聚烯烃弹性体膜内部交联生成空间网络，使聚烯烃膜的耐热性大幅度提高，便于使用、储存和运输，适于大规模推广应用。

Description

辐射交联的聚烯烃弹性体膜及其制备方法
技术领域
本发明涉及塑料膜的技术领域，特别涉及聚烯烃弹性体膜的技术领域，具体是指辐射交联的聚烯烃弹性体膜及其制备方法。
背景技术
辐射交联是利用各种辐射引发高分子聚合物高分子长链之间的交联反应的技术手段。辐射是指各种核辐射如电子束、γ射线、中子束、粒子束等等。光辐射如紫外光等可利用紫外光引发交联反应，称为光交联，其本质上讲也是一种辐射交联。高分子聚合物分子链与链之间缺乏紧密的结合力，使得整体材料在经受外力及环境温度影响时产生变形或发生破坏，限制了其应用。通过交联反应，聚合物高分子长链之间形成化学键等结合点，使聚合物的物理性能、化学性能获得改善，是一种非常有效的对高分子聚合物的改性手段。辐射交联指使用核辐射使高分子聚合物交联的手段。辐射交联时，聚合物本身与辐射发生装置没有物理接触，反应前后聚合物的形状也没有改变，但其内部已经发生了交联反应。聚合物可以直接将制品置于辐射线中发生交联反应，也可以在聚合物中添加交联助剂来促进辐射交联的效率。辐射交联目前较多的应用于热收缩管的生产，利用辐射后的塑料因交联而有了对形状的记忆能力，在室温下扩张经过辐射的塑料管，使其在受热情况下有回缩到原来形状的能力。另外一个使用较多的领域是汽车电线的生产，通过辐射交联使电线能够提高使用温度而满足使用于汽车发动机周围较热环境的要求。
聚烯烃弹性体具体指乙烯与丁烯、戊烯、己烯或辛烯的共聚物，最早由美国陶氏化学公司发明的以茂金属为催化剂具有相对较窄分子量分布和均匀短支链分布的弹性体乙烯和辛烯的共聚物。聚烯烃弹性体中的乙烯链结晶区作为物理交联点，长链的丁烯、戊烯、己烯或辛烯形成无定形的橡胶相，使其同时具有橡胶的弹性和塑料的热塑性的双重特性；其与聚烯烃特别是聚乙烯和聚丙烯相容性好，同时因没有不饱和键而耐候性好，其被大量的用于加工改性聚烯烃，比如改性聚丙烯的汽车零配件。聚烯烃弹性体的熔融温度较低，通常在50℃～70℃之间，所以通常极少单独使用。国内外很少有单独使用聚烯烃弹性体或者是把聚烯烃弹性体作为主要成份使用的报道。陶氏公司曾推出用聚烯烃弹性体和聚乙烯混合的聚烯烃弹性体胶膜作为替代太阳能光伏组件中常用的EVA胶膜；其中主要成份是聚烯烃弹性体，依靠高熔点的聚乙烯和低熔点的聚烯烃弹性体混合而使混合物的熔点峰值在100℃以上。专利CN103289582A中描述了聚烯烃弹性体在硅烷接枝后加入有机过氧化物制成膜，在使用时通过加热使过氧化物分解引发交联反应而提高聚烯烃弹性体的耐热性。由于聚烯烃弹性体的熔点非常低，即使是在加入高熔点的聚乙烯或者是加入交联剂，其弹性体部分的熔点依然十分低，在加热过程中弹性体会很快融化导致使用非常不方便或者由于熔点低而导致运输、储存温度要求苛刻，从而限制了其使用。如何提高聚烯烃弹性体膜本身的耐热性是一个重要的课题。
发明内容
为了克服上述现有技术中的缺陷，本发明的目的是提供一种辐射交联的聚烯烃弹性体膜，该发明设计巧妙，在聚烯烃弹性体膜被使用前，已经有了一定的交联度，从而提高了膜本身的耐热性，因此在存放、使用中由于熔点低而造成的很多问题迎刃而解。
本发明的另一个目的是提供一种上述辐射交联的聚烯烃弹性体膜的制备方法。
为了实现上述目的，本发明采用了如下的技术方案：
本发明提供了一种辐射交联的聚烯烃弹性体膜，包括以下重量份的组分：
Figure BDA0000468684880000021
所述聚烯烃弹性体为乙烯和丁烯、戊烯、己烯或辛烯共聚物中的一种或者几种的混合物，乙烯和丁烯、戊烯、己烯或辛烯的共聚物，因共聚种类不同或者乙烯含量的不同而区分出不同的级别。聚烯烃弹性体中可以适量加入聚乙烯，但由于聚乙烯和弹性体本身的乙烯完全融合而无法区分乙烯的来源。乙烯含量相同的混合物可以通过乙烯含量较低的弹性体加入适量的聚乙烯得到，也可以通过选择乙烯含量与前者相同的弹性体直接得到，所以适当加入聚乙烯不改变本描述的范围。
所述聚烯烃弹性体为经过极性基团接枝过的或不经过接枝的，在成膜时添加极性基团小分子添加剂；较佳地，极性基团为硅烷偶联剂；更佳地，硅烷偶联剂在弹性体成膜前已经接枝到弹性体分子链上的，其接枝率小于3%；优选为已接枝过乙烯基三甲氧基硅烷（A-171）的乙烯-己烯共聚物，接枝率为0.6%。
所述助交联剂是指多官能团的单体，可以是但不限于三烯丙基异氰脲酸酯（TAIC）、三聚氰酸三烯丙酯（TAC）、三羟甲基丙烷三丙烯酸酯（TMPTA）、三羟甲基丙烷三甲基丙烯酸酯（TMPTMA）等一种或几种。
所述抗氧剂是指抗热老化分解剂和紫外吸收剂，其可以但不限于酚类抗氧剂、受阻胺类抗氧剂、亚磷酸类、苯甲酮类、苯并三唑类等，例如：不限于四[β-（3，5-二叔丁基-4-羟基苯基）丙酸]季戊四醇酯（抗氧剂1010）、癸二酸二(2,2,6,6-四甲基-4-哌啶)酯（抗氧剂770）和N,N'-二仲丁基对苯二胺（抗氧剂4720）的一种或几种。
所述硅烷偶联剂指在分子中同时含有两种不同化学性质基团的有机硅化合物，优选为KH550；其经典产物可用通式YSiX3表示；其在塑料中通常用于提高塑料的粘结力或提高填充物的分散性。
所述有机过氧化物交联剂是指塑料常用的热交联用有机过氧化物交联剂，可以是但不限于过氧化二异丙苯（DCP）、过氧化-2-乙基己基碳酸叔丁酯（TBEC）、2，5-二甲基-2，5-双(叔丁基过氧基)己烷（双二五）等一种或几种。
所述颜料是指可以改变聚烯烃弹性体膜颜色的添加剂，可以是但不限于碳黑、锌钡白、硫化锌、钛白粉、玻璃微珠等。
所述辐射交联的聚烯烃弹性体膜的厚度为0.2～1mm；更佳的，厚度为0.3～0.7mm。
所述辐射交联的聚烯烃弹性体膜的交联度为3～70%。
本发明还提供了一种上述辐射交联的聚烯烃弹性体膜的制备方法，包括以下步骤：
将聚烯烃弹性体69～99.8份，助交联剂0.01～5份，抗氧剂0.01～2份，硅烷偶联剂0～2份，有机过氧化物交联剂0～2份和颜料0～20份，充分混合后加入挤出机，通过T形平板模具挤出成膜，经过辐射交联的方法得到辐射交联的聚烯烃弹性体膜。
所述辐射交联的方法中辐射交联指采用但不仅仅限于采用β射线（电子束）、γ射线（电磁波）、X射线（电磁波）、α射线（快速氦核流）或中子射线（不带电的粒子流）等辐射方法；辐射剂量为10～200KGY。
所述挤出机的温度为70～110℃，模具温度为70～110℃。
本发明同现有技术相比，具有以下优点和有益效果：
本发明通过将主要组分聚烯烃弹性体和有机过氧化物交联剂、助交联剂、硅烷偶联剂、抗氧剂和颜料等组分中的一种或几种的混合物挤出成膜后通过辐射交联使膜中形成交联的网络而提高膜本身的耐热性，使其便于使用、运输和储存，适于大规模推广应用。
具体实施方式
为了能够更清楚地理解本发明的技术内容，特举以下实施例详细说明。
实施例1
Figure BDA0000468684880000041
采用X射线进行辐射，辐射剂量为200KGY。
实施例2
Figure BDA0000468684880000042
采用电子束进行辐射，辐射剂量为50KGY。
实施例3
成分 重量份数
乙烯-辛烯共聚物 40
乙烯-丁烯共聚物 40
硫化锌 16.5
三烯丙基异氰脲酸酯（TAIC） 1
3-氨丙基三乙氧基硅烷（硅烷偶联剂KH550） 1
过氧化二异丙苯（过氧化物交联剂DCP） 1
N,N'-二仲丁基对苯二胺（抗氧剂4720） 0.5
采用电子束进行辐射，辐射剂量为10KGY。
分别按实施例1～3的配方将上述组分充分混合后加入挤出机，通过T形平板模具挤出成膜，经过所述的辐射和剂量进行辐射交联。挤出机温度、模具温度、厚度与玻璃的粘结力和交联度分别如下：
将实施例1～3制备得到的膜和对应的未经过辐射的同组分膜每种各取A4大小五张膜，分别叠好放入35℃的烘箱，上面放1000克的砝码，放置24小时后取出，比较粘连情况；发现辐射交联过的膜的粘连程度明显小于同组分未辐射交联的膜。
将实施例1～3制备得到的的膜和对应的未经过辐射的同组分膜每种各取1厘米宽长度为15厘米的样条5个，比较拉伸强度；发现所有经过辐射交联的膜的拉伸强度均比同组分未经辐射的膜高。
综上，本发明的辐射交联聚烯烃弹性体膜设计巧妙，利用辐射使膜达到一定的交联度，提高了膜本身的耐热性；辐射交联操作方便简易，交联后的膜便于使用、储存和运输，适于大规模推广应用。
在此说明书中，本发明已参照其特定的实施例作了描述。但是，很显然仍可以作出各种修改和变换而不背离本发明的精神和范围。

Claims (13)

1.一种辐射交联的聚烯烃弹性体膜，其特征在于：包括以下重量份的组分：
Figure FDA0000468684870000011
2.根据权利要求1所述的辐射交联的聚烯烃弹性体膜，其特征在于：所述聚烯烃弹性体为乙烯和丁烯、戊烯、己烯或辛烯共聚物中的一种或者几种的混合物。
3.根据权利要求2所述的辐射交联的聚烯烃弹性体膜，其特征在于：所述聚烯烃弹性体为经过极性基团接枝过的或不经过接枝的，在成膜时添加极性基团小分子添加剂；较佳地，极性基团为硅烷偶联剂；更佳地，硅烷偶联剂在弹性体成膜前已经接枝到弹性体分子链上的，其接枝率小于3%；优选为已接枝过乙烯基三甲氧基硅烷的乙烯-己烯共聚物，接枝率为0.6%。
4.根据权利要求1所述的辐射交联的聚烯烃弹性体膜，其特征在于：所述助交联剂是指多官能团的单体，可以是但不限于三烯丙基异氰脲酸酯、三聚氰酸三烯丙酯、三羟甲基丙烷三丙烯酸酯、三羟甲基丙烷三甲基丙烯酸酯一种或几种。
5.根据权利要求1所述的辐射交联的聚烯烃弹性体膜，其特征在于：所述抗氧剂是指抗热老化分解剂和紫外吸收剂，其可以但不限于酚类抗氧剂、受阻胺类抗氧剂、亚磷酸类、苯甲酮类、苯并三唑类，例如：不限于四[β-（3，5-二叔丁基-4-羟基苯基）丙酸]季戊四醇酯、癸二酸二(2,2,6,6-四甲基-4-哌啶)酯和N,N'-二仲丁基对苯二胺的一种或几种。
6.根据权利要求1所述的辐射交联的聚烯烃弹性体膜，其特征在于：所述硅烷偶联剂指在分子中同时含有两种不同化学性质基团的有机硅化合物，优选为KH550。
7.根据权利要求1所述的辐射交联的聚烯烃弹性体膜，其特征在于：所述有机过氧化物交联剂是指塑料常用的热交联用有机过氧化物交联剂，可以是但不限于过氧化二异丙苯、过氧化-2-乙基己基碳酸叔丁酯、2，5-二甲基-2，5-双(叔丁基过氧基)己烷一种或几种。
8.根据权利要求1所述的辐射交联的聚烯烃弹性体膜，其特征在于：所述颜料是指可以改变聚烯烃弹性体膜颜色的添加剂，可以是但不限于碳黑、锌钡白、硫化锌、钛白粉、玻璃微珠。
9.根据权利要求1所述的辐射交联的聚烯烃弹性体膜，其特征在于：所述辐射交联的聚烯烃弹性体膜的厚度为0.2～1mm；更佳的，厚度为0.3～0.7mm。
10.根据权利要求1所述的辐射交联的聚烯烃弹性体膜，其特征在于：所述辐射交联的聚烯烃弹性体膜的交联度为3～70%。
11.一种权利要求1至10任一所述的辐射交联的聚烯烃弹性体膜的制备方法，其特征在于：包括以下步骤：将聚烯烃弹性体69～99.8份，助交联剂0.01～5份，抗氧剂0.01～2份，硅烷偶联剂0～2份，有机过氧化物交联剂0～2份和颜料0～20份，充分混合后加入挤出机，通过T形平板模具挤出成膜，经过辐射交联的方法得到辐射交联的聚烯烃弹性体膜。
12.根据权利要求11所述的辐射交联的聚烯烃弹性体膜的制备方法，其特征在于：所述辐射交联的方法中辐射交联指采用但不仅仅限于采用β射线、γ射线、X射线、α射线或中子射线；辐射剂量为10～200KGY。
13.根据权利要求11所述的辐射交联的聚烯烃弹性体膜的制备方法，其特征在于：所述挤出机的温度为70～110℃，模具温度为70～110℃。
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