耐油橡胶防老剂的合成及其在丁腈橡胶中的应用

发布时间：2018-04-10 18:08

本文选题：丁腈橡胶 + 防老剂　；参考：《武汉大学》2017年硕士论文

【摘要】：国产油浸式变压器的漏、渗油问题一直比较严重,给我国的供电行业带来了巨大的安全隐患和经济损失。统计结果表明,导致这一现象的主要原因是橡胶密封材料的老化。变压器密封材料大多采用丁腈橡胶,尽管相对于其他常用的合成橡胶,丁腈橡胶性能优异,现有的橡胶配方和助剂也已经能够满足基本使用,但对于变压器恶劣环境下的使用不可避免的发生老化。因此对变压器用丁腈橡胶材料的改性尤为重要,通过改性可以在提高橡胶力学性能同时改善其耐老化性能。防老剂可以改善橡胶老化的现象,但对于高温或溶剂等恶劣的工作环境,普通防老剂往往因为挥发和抽出失去原有的防护效果。相比之下,大分子防老剂具有更加稳定的性能,这种防老剂不挥发、不迁移、不被抽出。大量的研究表明,将橡胶助剂与橡胶主体或者其它载体结合可以获得这种高效的橡胶助剂。本文通过硅烷偶联剂和对氨基二苯胺的反应合成了两种耐油密封橡胶防老剂,并使用两种防老剂改性白炭黑,通过相关表征考察了两种防老剂对白炭黑分散、表面性质的影响。实验结果表明,通过反应使白炭黑表面接枝上了对苯二胺基团,白炭黑表面羟基明显减少,同时对苯二胺类大分子使白炭黑具有了明显的疏水性质,接触角明显提高。本文将防老剂改性后的白炭黑添加于丁腈橡胶中,研究了 NBR硫化胶的物理机械性能和耐老化性能,并与防老剂4020和偶联剂KH 550进行了对比。实验结果表明,两种防老剂的偶联效果接近KH 550;相比于添加防老剂4020的NBR硫化胶,添加两种防老剂的NBR硫化胶耐空气老化性能和耐油老化性能明显提高,接枝防老剂的白炭黑在丁腈橡胶中的团聚现象明显改善。本文还考察了防老剂改性白炭黑的添加量对NBR硫化胶的物理机械性能和耐老化性能的影响。实验结果表明,白炭黑用量的增加会使硫化胶拉伸强度和硬度提高,使断裂伸长率和加工性能下降;硫化胶的耐空气老化性能和耐油性能也随着白炭黑用量增加而提高;但是随着白炭黑用量超过50份,用量对性能的影响不再明显。综合考虑下改性白炭黑的用量在40-50份左右最为合适。
[Abstract]:The leakage and oil leakage of oil-immersed transformer in China have been serious all the time, which has brought huge safety hidden trouble and economic loss to our country's power supply industry.The statistical results show that the main cause of this phenomenon is the aging of rubber sealing materials.Transformer sealing materials are mostly nitrile rubber, although compared with other commonly used synthetic rubber, nitrile rubber has excellent performance, existing rubber formulations and additives have been able to meet the basic use,However, the use of transformers under harsh conditions is inevitably aging.Therefore, the modification of NBR for transformer is particularly important, which can improve the mechanical properties of rubber and the aging resistance of NBR at the same time.Antioxidant can improve the aging phenomenon of rubber, but for the bad working environment such as high temperature or solvent, ordinary antioxidant often loses its original protective effect because of volatilization and extraction.By contrast, macromolecular antioxidants have more stable properties, which do not volatilize, do not migrate, and are not withdrawn.A large number of studies have shown that the rubber auxiliaries can be obtained by combining the rubber auxiliaries with the rubber host or other supports.In this paper, two kinds of oil-resistant rubber antioxidants were synthesized by silane coupling agent and p-aminodiphenylamine reaction, and two antioxidants were used to modify silica. The effects of two antioxidants on the dispersion and surface properties of silica were investigated by correlation characterization.The experimental results showed that the surface of silica was grafted with p-phenylenediamine group, the hydroxyl group of silica surface was decreased obviously, and the hydrophobic property and contact angle of silica were obviously improved by the macromolecule p-phenylenediamine.The physical and mechanical properties and aging resistance of NBR vulcanizate were studied by adding silica modified by antioxidant to nitrile butadiene rubber. The results were compared with antioxidant 4020 and coupling agent KH550.The results showed that the coupling effect of the two antioxidants was close to that of KH550.The air aging resistance and oil aging resistance of NBR vulcanizates with two antioxidants were significantly improved compared with those of NBR vulcanizates with antioxidant 4020.The agglomeration of silica grafted with antioxidant in nitrile rubber was obviously improved.The effects of the amount of silica modified by antioxidant on the physical and mechanical properties and aging resistance of NBR vulcanizate were also investigated.The results showed that the tensile strength and hardness of vulcanizate increased with the increase of silica content, and the elongation at break and processability decreased, and the air aging resistance and oil resistance of vulcanizate also increased with the increase of silica content.However, with the amount of silica more than 50 phr, the effect of the amount of silica on the performance is not obvious.The optimum dosage of modified silica was 40-50 phr.
【学位授予单位】：武汉大学
【学位级别】：硕士
【学位授予年份】：2017
【分类号】：TQ330.382

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