【作者】 舒雪桂；

【导师】 沈家祥； 陈立功；

【作者基本信息】 天津大学 ， 药物化学， 2005， 硕士

【摘要】 受阻胺类光稳定剂(HALS)是20世纪70年代末研制开发出的新型高效光稳定剂,其光稳定效果远好于传统光稳定剂。因此,自它问世以来一直是聚合物稳定化助剂领域中的研究热点。本文分别采用两步法和三步法合成路线对受阻胺类光稳定剂Cyasorb UV-3346和Chimassorb 2020的合成工艺进行了研究。结果表明Cyasorb UV-3346采用两步法合成工艺能得到产品的数均相对分子量为1600左右,分子量分布为2.0左右,在425nm下透光率大于95%,己二胺哌啶消耗低于0.85,各项指标均达到国外同类产品水平。目前Cyasorb UV-3346已经采用两步法合成工艺成功地进行了试生产。采用三步法合成Chimassorb 2020,得到产品的数均相对分子量为2600~3400,分子量分布小于1.5,而两步法不能得到令人满意的结果。在所建立的聚合型HALS合成工艺的基础上,本文设计合成了一类新型多功能高分子量稳定剂,这类稳定剂同时含有受阻胺和受阻酚功能基团,预期它们将同时具有光稳定和抗氧化的功能。本文以2,6-二叔丁基-4-甲基苯酚和3,5-二叔丁基-4-羟基苯甲醛为原料通过两条合成路线对所设计稳定剂的合成进行了研究。并以3,5-二叔丁基-4-羟基苯甲醛为原料,经亚胺化反应,亚胺产物的还原反应,再采用本文所建立的两步法合成工艺成功得到了目标化合物。产品数均相对分子量为2000~3000,分子量分布为2.0左右,在425nm下透光率小于60%,己二胺哌啶消耗约0.85左右。另外,在用NaBH4还原2,6-二叔丁基-4-(烷基亚胺基)甲基苯酚时发现,有副产物N,N-二(3,5-二叔丁基-4-羟基-苄基)-N-烷基胺生成。研究结果表明,这一副产物是由2,6-二叔丁基-4-(烷基胺基)甲基苯酚转化而来。为此,本文对这一反应提出了可能的反应机理。更多还原

【Abstract】 Hindered amine light stabilizers (HALS) are a new class of light stabilizers developed at the end of 1970s, which exhibited excellent light stabilizing performance much better than traditional stabilizers. Thus, the attractive research field was intensively studied during the last several decades.The two-step and three-step synthetic routes were employed for the synthesis of Cyasorb UV-3346 and Chimassorb 2020 in this paper. Cyasorb UV-3346 was successfully obtained by two-step synthetic process. The numerical average molecular weight was about 1600, the polydispersity was about 2.0, the transparency was over 95% under 425 nm and the consumption of N,N’-bis-(2,2,6,6-tetramethyl-4-piperidyl) -1,6-hexanediamine was about 0.85. Pilot scale production of it was qualified as the advanced level of the kindred products. Furthermore, Cyasorb UV-3346 has been successful according to two-step synthetic process. Chimassorb 2020 which had the numerical average molecular weight between 2600~3400 and the polydispersity lower than 1.5, was obtained by three-step synthetic process, but not by two-step synthetic route.Based on the established synthetic processes for polymeric HALS, a series of polymeric high molecular weight and multi-functional stabilizers with both of hindered amine group and hindered phenol group were designed in order to attain light stability and antioxidant functions. In this thesis, two synthetic routes for the target molecules started from 2,6-di-tert-butyl-4-methylphenol or 3,5-di-tert-butyl-4- hydroxy-benzaldehyde were studied respectively. The target molecules were successfully synthesized from 3,5-di-tert-butyl-4-hydroxy-benzaldehyde through imidation, reduction and the established two-step synthetic process. The numerical average molecular weight was between 2000 and 3000, the polydispersity was about 2.0, the transparency was lower than 60% under 425nm and the consumption of N,N’-bis-(2,2,6,6-tetramethyl-4-piperidyl)-1,6-hexanediamine was about 0.85.Additionally, several byproducts of N,N-bis-(3,5-di-tert-butyl-4-hydroxybenzyl)- N-alkylamines were obtained and determined in the reduction of 3,5-di-tert-butyl-4- ((alkylimino)-methyl)-phenol with NaBH4. Designed experimental results they were formed from the 2,6-di-tert-butyl-4-alkylaminomethyl-phenol. The possible mechanism of this transformation was proposed in the thesis.更多还原