【作者】 董传明；

【导师】 陈立功；

【作者基本信息】 天津大学 ， 应用化学， 2005， 博士

【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,表现出优异的光稳定性和应用性能,且与紫外线吸收剂和抗氧剂有良好的协同效应,因此受到广泛的关注,是近二、三十年来国内外研究最活跃的领域之一。根据三聚氯氰的结构特点,本文设计了两步法、三步法和四步法三条不同的合成路线,并首先对Chimassorb 944的合成进行了系统研究。两步法是通过胺取代三聚氯氰环上的一个氯原子得到中间体I,然后中间体I与己二胺哌啶一起投入高压釜,采用分段升温的方法制得所需聚合物;三步法是分三步采用不同反应条件依次取代三聚氯氰环上的三个氯原子以制得所需聚合物;四步法是通过中间体I分别与己二胺哌啶在常温和高压釜中反应得到两个中间体,然后这两个中间体再进行聚合反应得到目标产物。研究结果表明,两步法简单易行,采用此合成路线制得的Chimassorb 944数均相对分子量为2000~3000,分子量分布为2.0左右,在425nm下透光率大于95%,己二胺哌啶消耗约0.80左右,达到了国外同类产品水平。然后本文又采用此合成路线成功制得了Cyasorb UV-3346,产品数均相对分子量为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,也达到了国外同类产品水平。由于Chimassorb 2020要求分子量分布很窄,采用两步法合成路线不能得到满意的产品,针对Chimassorb 2020的结构特点,本文采用三步法制得了数均相对分子量为2600~3400,分子量分布小于1.5的产品。在聚合型HALS合成工艺已建立的基础上,本文又设计了两个同时含有受阻胺和受阻酚活性基团的新型多功能聚合型高分子量稳定剂,预期它同时具有抗光氧化和抗热氧化的功能。本文分别以4-甲基-2,6-二叔丁基苯酚和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所设计的多功能稳定剂。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。在2004年,Chimassorb 944已经采用两步法合成工艺实现了工业化生产。目前Cyasorb UV-3346正在采用两步法合成工艺进行试生产。更多还原

【Abstract】 Hindered amine light stabilizer (HALS) is a new class of excellent light stabilizerdeveloped at the end of 1970s. They have shown excellent light stabilizing ability,application performance and synergism with ultraviolet absorbers and antioxidants.Thus, extensive attention has been paid to this area, which has become the mostattractive research field during the last several decades.According to the characteristics of cyanuric chloride, three different syntheticprocesses, namely two-step, three-step and four-step processes, for synthesis ofChimassorb 944 were designed and examined systematically in this thesis. Accordingto the two-step synthetic process, the intermediate I, which was obtained from thesubstitution of one chlorine atom on triazine ring with amine, was charged into anautoclave together with N,N’-bis-(2,2,6,6-tetramethyl-4-piperidyl)-1,6-hexanediamine. The desired polymer was obtained by programmed temperature.Three chlorine atoms on triazine ring were substituted one by one under differentreaction conditions in three-step synthetic process and the desired polymer wasobtained. However, according to the four-step synthetic process, two intermediatewere obtained by treatment of the intermediate I with N,N’-bis-(2,2,6,6-tetramethyl-4-piperidyl)-1,6-hexanediamine at low temperature and at high temperature in anautoclave respectively. Condensation of these two obtained intermediates in anautoclave afforded the target polymer. The results indicated that the two-step syntheticprocess was more efficient. The obtained Chimassorb 944 was qualified as theadvanced level of the kindred products. The numerical average molecular weight wasbetween 2000 and 3000, the polydispersity was about 2.0, the transparency was over95% under 425nm and the consumption ofN,N’-bis-(2,2,6,6-tetramethyl-4-piperidyl)-1,6-hexanediamine was about 0.80.Similarly, qualified Cyasorb UV-3346 was successfully obtained by two-stepsynthetic process. The numerical average molecular weight was about 1600, thepolydispersity was about 2.0, the transparency was over 95% under 425nm and theconsumption of N,N’-bis-(2,2,6,6-tetramethyl-4-piperidyl)-1,6-hexanediamine wasabout 0.85. Because the polydispersity of Chimassorb 2020 was lower than 1.5, thesatisfied product could not be made by two-step synthetic route. According to thecharacteristics of Chimassorb 2020, the product, which had the numerical averagemolecular weight between 2600~3400 and the polydispersity lower than 1.5, wassuccessfully obtained by three-step synthetic process.Based on the established synthetic processes for polymeric HALS, two novelpolymeric high molecular weight and multi-functional stabilizers with hindered amineand hindered phenol as active groups together were designed in order to attain lightstability and antioxidant functions.In this thesis, two synthetic routes for the target molecules started from2,6-Di-tert-butyl-4-methylphenol or 3,5-Di-tert-butyl-4-hydroxy-benzaldehyde werestudied respectively. The designed products were successfully synthesized from3,5-Di-tert-butyl-4-hydroxy-benzaldehyde through imidation, reduction and theestablished two-step synthetic process. The numerical average molecular weight wasbetween 2000 and 3000, the polydispersity was about 2.0, the transparency was lowerthan 60% under 425nm and the consumption ofN,N’-bis-(2,2,6,6-tetramethyl-4-piperidyl)-1,6-hexanediamine was about 0.85.Industrial production of Chimassorb 944 had already been operated according toestablished two-step synthetic process in 2004. Furthermore, Cyasorb UV-3346 isdoing trial-production according to two-step synthetic process.更多还原