高性能橡胶复合材料的制备及性能研究

发布时间：2018-11-24 18:14

【摘要】：随着雾霾在全国频发,国内对于环保节能需求更加紧迫,其中汽车节能减排更是重中之重。为此近几年“绿色轮胎”概念在汽车工业兴起,开发高性能、低滚动阻力轮胎成为行业研发重点。橡胶配方中的填料对橡胶强度、滚动阻力、抗湿滑性起着至关重要作用。本课题以开发高补强、低滚动阻力的填料为目标,从开发间同1,2-聚丁二烯(s PBD)类新型填料以及对白炭黑改性两方面入手,制备了高强度、低滚动阻力橡胶复合材料,主要研究内容及结论如下:1、新型填料s PBD开发:合成了一系列新型的磷酸酯类化合物,并作为给电子体应用于铁系催化剂。详细地研究了给电子体的结构以及聚合条件对聚合活性及产物微观结构和性能的影响。以磷酸酯类为给电子体的催化剂在三异丁基铝的活化下,在正己烷溶剂中可实现高效地催化丁二烯聚合,合成高1,2-含量和结晶度可调的s PBD,同时此催化体系的热稳定性优异。溶液聚合所获得s PBD对顺丁橡胶具有优异补强效果,10 wt%添加量下相比炭黑补强,拉伸强度提高2倍,断裂伸长率提高3倍。但溶液聚合的s PBD颗粒大,添加量增大后不利于在顺丁橡胶中分散,为解决该问题本课题后续以POSS为载体开发了负载聚合,获得微米级s PBD悬浮液,利用该悬浮液与顺丁橡胶共混,可在s PBD高添加量情况下依然能获得分散良好的混合胶。负载s PBD产物能大幅度改善了顺丁橡胶的拉伸强度和100%定伸强度,力学性能改善同时相比炭黑补强,s PBD补强橡胶还具有更低的滚动阻力。2、改性白炭黑:本课题通过烯烃复分解方式合成端基带硅氧烷官能团的顺丁橡胶遥爪聚合物,并详细研究对复分解反应影响因素。再将遥爪聚合物改性白炭黑,改性后白炭黑键合上顺丁橡胶,能够大幅度改善白炭黑在有机溶剂和顺丁橡胶中分散。这种优异分散,虽然略微降低了补强橡胶的强度,但在硫化效抗湿滑性和滚动阻力上均获得了明显的改善。
[Abstract]:With the frequent occurrence of haze in China, the demand for environmental protection and energy saving is more urgent in China, especially for automobile energy saving and emission reduction. In recent years, the concept of "green tire" has emerged in the automobile industry. The development of high performance and low rolling resistance tires has become the focus of research and development in the industry. The filler in rubber formulation plays an important role in rubber strength, rolling resistance and wet-slip resistance. In this paper, the high strength and low rolling resistance rubber composites were prepared by developing high strength and low rolling resistance fillers, starting with the development of new (s PBD) fillers and the modification of silica. The main research contents and conclusions are as follows: 1. A series of new phosphate compounds were synthesized and used as electron donor in iron catalyst. 1. The development of new filler s PBD. The effects of the structure of the electron donor and the polymerization conditions on the polymerization activity and the microstructure and properties of the product were studied in detail. Under the activation of triisobutyl aluminum, the catalyst with phosphate ester as electron donor can efficiently catalyze the polymerization of butadiene in n-hexane solvent to synthesize s PBD, with high content of 1 ~ (2 +) and adjustable crystallinity. At the same time, the thermal stability of the catalyst system is excellent. S PBD obtained by solution polymerization had excellent reinforcing effect on cis-butadiene rubber. Compared with carbon black, the tensile strength and elongation at break of 10 wt% were 2 times and 3 times higher than that of carbon black respectively. However, because of the large amount of s PBD particles in solution polymerization, the increase of the addition amount is not conducive to dispersion in cis-butadiene rubber. In order to solve this problem, the supported polymerization was developed with POSS as the carrier to obtain the micrometer s PBD suspension. When the suspension was blended with cis-butadiene rubber, a well-dispersed blend could be obtained under the condition of high addition of s PBD. The tensile strength and 100% tensile strength of cis-butadiene rubber were greatly improved by loading s PBD products. The mechanical properties were improved and the rolling resistance of, s PBD reinforced rubber reinforced by carbon black was also lower than that of, s PBD reinforced with carbon black. Modified silica: the cis-butadiene telomeric polymer with siloxane functional groups at the end of the base was synthesized by the method of olefin double-decomposition, and the factors affecting the reaction were studied in detail. Then modified silica with telomeric polymer and modified silica bonded with cis-butadiene rubber can greatly improve the dispersion of silica in organic solvents and cis-butadiene rubber. Although the excellent dispersion slightly reduced the strength of the reinforced rubber, the wet slip resistance and rolling resistance of the vulcanization effect were obviously improved.
【学位授予单位】：宁波大学
【学位级别】：硕士
【学位授予年份】：2017
【分类号】：TB332

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