CN103788515B - 一种高气体阻隔性能热塑性硫化胶及其制备方法 - Google Patents
一种高气体阻隔性能热塑性硫化胶及其制备方法 Download PDFInfo
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Abstract
本发明涉及一种高气体阻隔性能热塑性硫化胶及其制备方法,属于高分子材料技术领域。由预先与增容剂共混接枝的尼龙和丁基橡胶组成的橡塑共混物通过动态硫化制得,增强了尼龙和橡胶之间的界面相容性,使得到的热塑性硫化胶气体阻隔性能、力学性能、质量和硬度等均能满足轮胎气密层材料的要求。
Description
技术领域
本发明涉及一种高气体阻隔性能热塑性硫化胶及其制备方法,属于高分子材料技术领域。
背景技术
热塑性弹性体是常温下具有橡胶的弹性,高温下可塑化成型的一类弹性体。热塑性硫化胶是热塑性弹性体的一种,是通过橡塑共混经动态全硫化制得的一类材料。在混炼机械的高速剪切应力作用下,共混体系发生相反转,被硫化的橡胶以颗粒的形式分散在作为连续相的塑料相中。
丁基橡胶和尼龙都是气密性优异的材料,两者混合通过动态硫化制得的热塑性硫化胶具有较好的物理性能以及优异的气密性,主要应用于轮胎的气密层。与传统的热固性轮胎气密层相比,其质量更轻,气密性更好。加拿大西三一大学的VanDykeJD研究了丁基橡胶与尼龙12通过动态硫化制备的热塑性硫化胶(TPV),发现氯化丁基橡胶(CIIR)与尼龙12用硫磺硫化体系制得的热塑性硫化胶具有较优异的力学性能。但是其存在以下问题:一、CIIR会对环境产生污染,将来的丁基橡胶市场将以溴化丁基橡胶(BIIR)为主;二、硫磺硫化体系存在容易返原的问题,不利于热塑性硫化胶的重复加工使用。
作为轮胎气密层材料,需要具有一定的力学强度,同时硬度又不能太高,尤为重要的是具有优异的气体阻隔性能。专利CN102964702A公布了一种高气体阻隔性能的热塑性硫化胶的制备方法,其所用橡胶为BIIR,尼龙为三元共聚尼龙,在密炼机中热混,分别加入了氯化聚乙烯(CPE)、(马来酸酐接枝的聚乙烯辛稀共聚物)POE-g-MAH作为增容剂,但是增容效果并不理想,虽然动态硫化后得到了硬度比较低的热塑性硫化胶,但是橡胶相的分散粒径很大,同时此专利也未给出具体的气体阻隔性能数据。专利CN103030895A公布了一种高气体阻隔性能的热塑性硫化胶及其制备方法,其所用橡胶为CIIR,尼龙为尼龙12,通过自制增容剂(氯化丁基橡胶、聚异丁烯、马来酸酐的“自制预混物”),在双螺杆中动态硫化制得力学性能和气体阻隔性能较优异的热塑性硫化胶,但是自制增容剂的制备过程比较繁琐,消耗人力物力,不利于实现工业化生产。
发明内容
本发明的目的是提供一种高气体阻隔性能热塑性硫化胶及其制备方法。由预先与增容剂共混接枝的尼龙和丁基橡胶组成的橡塑共混物通过动态硫化制得,增强了尼龙和橡胶之间的界面相容性,使得到的热塑性硫化胶气体阻隔性能、力学性能、质量和硬度等均能满足轮胎气密层材料的要求。
本发明一种高气体阻隔性能热塑性硫化胶的基本组成和质量份数为:
所述的溴化丁基橡胶最好选用门尼粘度ML(1+8)125℃:30-40的溴化丁基橡胶,其硫化速度快,适合螺杆动态硫化时间短的要求;
尼龙为尼龙12,最好选用熔融指数为230℃2.16kg1-10g/10min的尼龙12,尼龙12熔点低,吸水率低,硬度也较低,动态硫化可减缓BIIR的降解;
抗氧剂为受阻酚类抗氧剂,优选抗氧剂1010;
稳定剂为环氧大豆油/硬脂酸钙/受阻酚类抗氧剂的复合体系,其中环氧大豆油、硬脂酸钙、受阻酚类抗氧剂的质量比为1.5-4:1.5-3:0.5-2.5;稳定剂中的受阻酚类抗氧剂优选抗氧剂1010;稳定剂的加入是为了避免溴化丁基橡胶高温的降解;
硫化助剂为(HVA-2);
增容剂为聚异丁烯丁二酸酐(PIBSA)或聚丙烯接枝马来酸酐(PP-g-MAH)(最好选用马来酸酐接枝率为1.2%-2%的聚丙烯接枝马来酸酐)或两者的混合物:PIBSA酸酐基团可与尼龙12的氨基基团发生反应,而另一端聚异丁烯与溴化丁基橡胶相容性极佳;PP-g-MAH作为增容剂,其酸酐接枝率很高,增容效果也很理想。
增塑剂为石蜡油;
本发明加入N-丁基苯磺酰胺的目的是降低产品的硬度,优选的加入份数为10-25份。
本发明还提供了一种高气体阻隔性能热塑性硫化胶的制备方法,其特征是具体步骤为:
A、增容剂与尼龙在密炼机中175-200℃共混接枝5-10min;
B、将稳定剂加入溴化丁基橡胶中混合均匀,再与步骤A的产物、抗氧剂在175-200℃下,混合均匀,降至室温,加入氧化锌、硬脂酸、硫化助剂和增塑剂;
C、将步骤B得到的共混物置于双螺杆挤出机中,设置各节螺杆温度为170℃-200℃(保证尼龙完全熔融,且与BIIR的硫化温度相匹配),转速为300-600rpm(转速太高,硫化时间短,不利于交联;转速太低,不利于剪切破碎),完成动态硫化过程,得到高气体阻隔性能热塑性硫化胶。
为降低产品的硬度,还可向步骤C的产物中加入N-丁基苯磺酰胺(N-BBSA)混合均匀,得到本发明所述高气体阻隔性能热塑性硫化胶。
本发明的特点是:
本发明采用了溴化丁基橡胶复合稳定体系,与只用受阻酚类抗氧剂作为稳定剂相比,稳定效果更佳,有效降低了溴化丁基橡胶在尼龙12加工温度下的降解。
尼龙是一种极性塑料,而溴化丁基橡胶橡胶是一种非极性橡胶,两者相容性很差。本发明采用聚异丁烯丁二酸酐(PIBSA)作为增容剂,其酸酐基团可与尼龙的氨基基团发生反应,而另一端聚异丁烯与溴化丁基橡胶相容性极佳;聚丙烯接枝马来酸酐(PP-g-MAH)作为增容剂,其酸酐接枝率很高,增容效果也很理想。
加工工艺方面,增容剂先与尼龙共混接枝,大大地增强了界面之间的结合,起到了很好的增容效果,有效地提高了体系的力学性能;动态硫化结束后,加入N-BBSA,调节产品的硬度和柔软性,增加流动性,既不影响动态硫化,又不影响剪切破碎。
附图说明:
图1、图2为本发明实施例2热塑性弹性体的扫描电镜背散射照片,图中:深色部分为橡胶相,浅色部分为塑料相。从图1中可以看出橡胶相分散均匀,从图2可以看出分散相粒径大约为3-4um。
具体实施方案:
下边结合具体实施例,对本发明做进一步详细说明。实施例中的拉伸强度、断裂伸长率、绍尔A型硬度分别按下列标准GB/T528-2009、GB/T528-2009、GB/T531.1-2008测定。透气系数按ISO2782标准自制自动化气密性测试仪进行气体阻隔性能测试。
实施例1:(实施例中所述的份均为质量份)
尼龙12(熔融指数230℃2.16kg,3.5g/10min)在120℃烘干5个小时,将尼龙12(54份)与增容剂聚异丁烯丁二酸酐PIBSA(10份)在185℃下熔融接枝10min;将稳定体系(环氧大豆油:硬脂酸钙:抗氧剂1010=2:2:1)(5份)加入到BIIR(门尼粘度ML(1+8)125℃:32)(100份)中,将BIIR与稳定剂的混合物与接枝共混物、抗氧剂1010(1份),于185℃在密炼机中混合均匀。温度降至室温,将氧化锌(2份)、硫化助剂HVA-2(4份)、硬脂酸(1.2份)和石蜡油(15份)加入到上述混合物中。
在双螺杆挤出机(HTS-40,南京橡塑机械厂)中进行动态交联。设置各节螺杆/机头温度185185185185185185185185185185185185/185,双螺杆转速为480rpm。出料,测性能。
实施例2:
采用聚丙烯接枝马来酸酐PP-g-MAH作为增容剂,其他制备过程同实施例1。
对比例1:
不加入增容剂,其他制备过程同实施例1。
表1
表1中的数据显示,增容剂的加入大大提高了热塑性硫化胶的力学性能,并且气密阻隔性能也得到了明显的提高;与PIBSA增容相比,PP-g-MAH增容得到的力学性能更加优异,气体阻隔性能也较好。
实施例3:
尼龙12(同实施例1)在120℃烘干5个小时,将尼龙12(43份)与PIBSA增容剂(5份)于190℃熔融接枝7.5min;将稳定剂(环氧大豆油:硬脂酸钙:抗氧剂1010=3:2.5:1.5)(7份)加入到BIIR(同实施例1)(100份)中,称取BIIR与稳定剂的混合物与接枝共混物、抗氧剂1010(1.5份),于190℃在密炼机中混合均匀。温度降至室温,将氧化锌(3份)、硫化助剂HVA-2(3份)、硬脂酸(1.5份)和石蜡油(20份)加入到上述混合物中。
在实施例1所述的双螺杆挤出机中进行动态交联,设置各节螺杆/机头温度185185185185185185185185185185185185/185,双螺杆转速为480rpm。完成动态交联后,加入N-BBSA调节硬度,测性能。
对比例2:
增容剂为PIBSA,不加入N-BBSA;其他制备过程同实施例3。
对比例3:
增容剂为PP-g-MAH,不加入N-BBSA;其他制备过程同实施例3。
实施例4:
增容剂为PP-g-MAH,加入N-BBSA调节硬度;其他制备过程同实施例3。
表2
表2中的数据显示,不管是加入增容剂PIBSA,还是PP-g-MAH,N-BBSA的加入都使体系的硬度大大下降,满足了轮胎气密层材料的使用条件。
实施例5:
尼龙12(同实施例1)在120℃烘干5个小时,将尼龙12(67份)与增容剂PP-g-MAH(15份)于195℃熔融接枝5min;稳定剂(环氧大豆油:硬脂酸钙:抗氧剂1010=4:3:2)加入到BIIR(同实施例1)(100份)中,将BIIR与稳定剂的混合物与接枝共混物、抗氧剂1010(2份),于195℃在密炼机中混合均匀。温度降至室温,将氧化锌(3份)、硫化助剂HVA-2(3份)、硬脂酸(1.5份)和石蜡油(25份)加入到上述混合物中。
在实施例1所述的双螺杆挤出机中进行动态交联。各节螺杆/机头温度为175175180180180185185185185185185185/185,双螺杆转速为300rpm。
完成动态交联后,加入N-BBSA(20份)调节硬度。测性能。
实施例6:
在实施例1所述的双螺杆挤出机中进行动态交联。各节螺杆/机头温度为180180185185185190190190190190190190/190,双螺杆转速为450rpm。其他制备过程同实施例5。
实施例7:
在实施例1所述的双螺杆挤出机中进行动态交联。各节螺杆/机头温度185185190180190195195195195195195195/195,双螺杆转速为550rpm。其他制备过程同实施例5。
表3
表3的数据显示,相对较低的动态硫化温度配合较低的剪切速率(转速),得到的力学性能和气体阻隔性能更加优异。
Claims (5)
1.一种高气体阻隔性能热塑性硫化胶,其基本组成和质量份数为:
其特征在于,增容剂为聚丙烯接枝马来酸酐;稳定剂为环氧大豆油/硬脂酸钙/受阻酚类抗氧剂的混合物,其中环氧大豆油、硬脂酸钙、受阻酚类抗氧剂的质量比为1.5-4:1.5-3:0.5-2.5。
2.根据权利要求1的高气体阻隔性能热塑性硫化胶,其特征在于,所述的尼龙为尼龙12。
3.根据权利要求1的高气体阻隔性能热塑性硫化胶,其特征在于,所述的抗氧剂为受阻酚类抗氧剂。
4.根据权利要求1的高气体阻隔性能热塑性硫化胶,其特征在于,所述的硫化助剂为HVA-2。
5.权利要求1至4任何一种高气体阻隔性能热塑性硫化胶的制备方法,其特征是具体步骤为:
A、增容剂与尼龙在密炼机中175-200℃共混接枝5-10min;
B、将稳定剂加入溴化丁基橡胶中混合均匀,再与步骤A的产物、抗氧剂在175-200℃下,混合均匀,降至室温,加入氧化锌、硬脂酸、硫化助剂和石蜡油;
C、将步骤B得到的共混物置于双螺杆挤出机中,设置各节螺杆温度为170℃-200℃,转速为300-600rpm,完成动态硫化过程,然后向得到的硫化胶中加入N-丁基苯磺酰胺,混合均匀,得到高气体阻隔性能热塑性硫化胶。
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