摘要
溴化丁基橡胶(BIIR)具有低透气性、耐老化性、耐臭氧性及耐化学药品性等优异性能,所以它被用于制造轮胎、药品瓶塞等工业产品。蒙脱土(MMT)是一种层状的硅铝酸盐,通过有机改性,能使有机化的硅酸盐与多数聚合物具有良好的相容性,从而有利于聚合物和单体的嵌入,是插层法制备纳米复合材料的关键方法之一。
本研究选用BIIR作为基体材料,用原位有机改性的方法,将不同有机改性剂和MMT应用到BIIR中,制得溴化丁基橡胶/有机蒙脱土(BIIR/OMMT)纳米复合材料。研究了其硫化特性、力学性能、热分解行为和微观形态结构。
采用原位有机改性的方法制备了溴化丁基橡胶/有机蒙脱土复合材料,研究了该复合材料的力学性能。结果发现,各种有机蒙脱土对溴化丁基橡胶都具有一定的补强作用,且使用原位有机改性方法制备的复合材料,在减少有机土预处理的同时,其力学性能达到并优于直接添加有机蒙脱土的复合材料。
应用无转子硫化仪研究了溴化丁基橡胶纯胶、溴化丁基橡胶/蒙脱土、溴化丁基橡胶/原位有机改性蒙脱土的硫化特性,并进行了比较。结果表明,直接添加OMMT和含有原位有机改性蒙脱土的混炼胶与添加Na-MMT的混炼胶相比,胶料的焦烧时间和正硫化时间缩短,最低转矩与最高转矩的差值明显增加。原位有机改性方法制得的复合材料,其硫化反应表观活化能较添加蒙脱土的混炼胶和纯胶的有一定程度的降低。
研究发现,溴化丁基橡胶/有机蒙脱土复合材料有良好的耐有机溶剂的性质。因此研究了插层剂用量和蒙脱土用量对于复合材料在其良溶剂二甲苯中的溶胀速度和程度,并与BIIR纯胶和BIIR/Na-MMT复合材料进行比较。结果表明,与纯胶和BIIR/Na-MMT复合材料相比,原位有机改性BIIR/OMMT纳米复合材料对二甲苯的吸收速度和吸收率降低。随着插层剂的增加,复合材料耐有机溶剂的性能提高。
同时,采用X射线衍射(XRD)、透射电子显微镜(TEM)和热重分析(TGA)表征了复合材料的微观形态结构和热稳定性。XRD表明,给BIIR/Na-MMT配合体系中分别加入不同插层剂,对Na-MMT进行原位有机处理之后,硫化胶中蒙脱土001晶面的层间距有了明显扩大,比有机蒙脱土的层间距还要大1.5nm左右。采用TGA分析了硫化胶的热稳定性,结果表明:加入插层剂后,硫化胶的热分解起始温度有一定的升高,说明Na-MMT和插层剂对提高BIIR的热分解温度具有协同效应,该效应主要来自蒙脱土粒子在BIIR中的良好分散。TEM证明了原位有机改性方法能制备出纳米型复合材料,且MMT能均匀分散在橡胶基体中。
Bromobutyl Rubber (BIIR) is used in manufacturing tyres, bottle stop for medicine etc., because of its excellent properties of low ventilation, anti-age property, anti-ozone and chemicals restriction. Montmorillonite (MMT) is a clay and consists of two fused silicate tetrahedral sheets sandwiching an edge-shared octahedral sheet of either magnesium or aluminum hydroxide. It has good compatibility with most polymers through organic modification, so that it will be easy for inset of polymers and monomers. And this is the key method of preparing nanocomposites.
In this study, BIIR was selected as matrix. In situ organic modification method was applied to use intercalatant and MMT into BIIR to make BIIR/OMMT composites. The vulcanization characteristics, mechanical property, thermal degradation behavior and microstructure of these composites were studied.
BIIR/OMMT composites were prepared by in situ organic modification and its mechanical properties were studied. The results showed that different kinds of organic MMT had certain reinforcement on BIIR and using the method of in situ organic modification can save the time of preparation of OMMT and the mechanical properties of these kind of BIIR/OMMT was equal to and even better than the composites by directly adding organic MMT.
The vulcanization characteristics of gum BIIR, BIIR/Na-MMT and BIIR/in situ OMMT composites were studied and compared by an oscillating disk rheometer. The results showed that, compared with adding only Na-MMT, adding directly OMMT and in situ organic modified OMMT have lower scorch time and vulcanization time. And the difference between maximum torque and minimum torque increased obviously. Composites prepared by in situ organic modification have lower apparent activation energy than adding Na-MMT and gum BIIR.
It was found that BIIR/OMMT has good restriction to organic solution. The effect of the content of intercalatant and MMT on the absorption speed and degree of the composites in dimethylbenzene was studied and compared with gum BIIR and the traditional BIIR/Na-MMT composites. The results showed that compared with BIIR and BIIR/Na-MMT, in situ organic modification BIIR/OMMT composites has lower swelling rate. And with the increase of intercalatant, the organic solvent restriction of the composites increased.
Meanwhile, XRD, TEM and TGA were used to investigate the morphology and thermal stability of the composites. According to XRD, adding different kind of intercalatants into BIIR/Na-MMT and after in situ organic modification for Na-MMT, the layer of MMT in the vulcanizate was expanded largely, which was about 1.5nm larger than the layer of MMT. TGA was used to analyze the thermal stability. The results showed that the beginning temperature of thermal degradation increased, which indicated Na-MMT and intercalatant had the cooperation effect on thermal temperature of BIIR. This effect mainly comes from the good dispersion of MMT particles in BIIR. TEM proved in situ organic modification method can prepare nanocomposites and MMT can disperse uniformly in the rubber matrix.
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