受阻胺光稳定剂

本文介绍第4代光稳定剂——受阻胺光稳定剂的结构、合成、效率和其光稳定化作用机理,并介绍受阻胺光稳定剂的未来发展.本文可供从事高分子工业的科研、生产、助剂合成及高分子材料的老化与防老化的研究工作者参考.     

高分子受阻胺光稳定剂存在下聚丁二烯的单线态氧氧化

用粘度法、ESR、IR、GPC等方法研究了三种商品高分子受阻胺存在下聚丁二烯的单线态氧氧化,结果表明,高分子受阻胺抑止聚丁二烯的单线态氧氧化,其效率是944>PDS>770>622。用Monroe方法测定了受阻胺对单线态氧的猝灭速率常数,K_q~(-O_2),它们是944(3.2×10~6M~(-1)s~(-1)),PDS(8.2×10~5M~(-1)s~(-1)),622,770为2×10~5M~(-1)s~(-1),ESR研究表明,在本实验条件下,944和PDS能够产生稳定的氮氧自由基No,而622则不产生。用GPC研究还发现,在本实验条件下,PDS具有对聚丁二烯的接枝——交联效应,提出了这种接枝交联效应的机理。     

受阻胺光稳定剂Chimassorb 119的合成

以N-丁基-2,2,6,6-四甲基-4-哌啶胺和2,4,6-三氯-1,3,5-三嗪为起始原料,经取代、甲基化反应后,与N,N′-二-（3-氨丙基）乙二胺进行亲核取代反应合成了受阻胺光稳定剂Chimassorb 119,总收率可达77.1 %,其结构经¹H NMR和ESI-MS确证。     

纳米级金红石型二氧化钛与受阻胺光稳定剂协同改进ABS的抗老化性能研究

分别采用纳米级金红石型TiO2和受阻胺光稳定剂(HALS)对ABS进行改性,通过熔融共混法制备了ABS/纳米TiO2、ABS/纳米TiO2/HALS和ABS/HALS复合材料,采用GB/T16422.2~1999所述的塑料实验室光源暴露实验方法,用氙灯气候试验机对其进行28天人工加速老化,通过测定其老化过程中的无缺口和缺口试样冲击强度的变化来对其抗老化性能进行表征,同时利用光学显微镜和扫描电镜对其老化过程中的冲击断口形貌变化进行了研究.结果表明,纳米TiO2在ABS基体中分散良好,改性后的复合材料均具有较好的抗老化性能,纳米TiO2与HALS复合改性ABS对其耐候性的提高具有明显的协同作用,其老化后的抗冲击性能超过了单一使用HALS或纳米TiO2的改性效果,老化28天后纯ABS树脂试样的无缺口冲击强度保持率只有20%左右,添加2.0 wt%纳米TiO2后,老化28天后的ABS/纳米TiO2/HALS复合材料试样的保持率则提高到47.9%,为纯ABS树脂试样的2.5倍.     

衍生化高效液相色谱法测定高分子受阻胺光稳定剂

以对硝基苯甲酰氯为酰基化试剂,通过与含胺基的高分子受阻胺光稳定剂944在四氢呋喃中发生酰胺化反应形成沉淀,改变反应配比确定对硝基苯甲酰氯与高分子受阻胺光稳定剂944反应比例为5∶1。利用傅立叶红外光谱分析反应沉淀来实现高分子受阻胺光稳定剂944的定性分析,利用高效液相色谱分析反应上层清液,实现定量分析,紫外可见检测器检测波长为360 nm,反应测试结果回收率可达到90%以上。     

新型受阻胺光稳定剂3-（2，2，6，6-四甲基哌啶4-氨基）丙酸十二酯的合成

建立了受阻胺光稳定剂3-(2,2,6,6-四甲基哌啶-4-氨基)丙酸十二酯的合成工艺.以2,2,6,6-四甲基-4-哌啶胺、丙烯酸甲酯为原料,经M ichael加成,生成的3-(2,2,6,6-四甲基哌啶-4-氨基)丙酸甲酯再与十二醇进行酯交换反应制得.并对所涉及的酯交换反应的工艺参数进行了优化.实验结果表明,四异丙基钛酸酯催化剂的催化效果最好;在3-(2,2,6,6-四甲基哌啶-4-氨基)丙酸甲酯与十二醇的摩尔比为1∶1.10,四异丙基钛酸酯催化剂的用量为反应物总质量的0.30%,反应温度180℃,反应时间8 h的条件下,酯交换反应收率为90.6%.该工艺总收率为86.3%.目标产物及中间体的结构通过MS进行了表征.     

双功能受阻胺光稳定剂GW-540与紫外线吸收剂并用效应的研究

本文用IR、UV、SEM等方法,研究了双功能基受阻胺光稳定剂——三(1,2,2,6,6-五甲基-4-哌啶基)亚磷酸酯(GW-540),与紫外线吸收剂UV-531、UV-327并用时对聚丙烯的防光作用,结果表明:GW-540-UV-531并用体系有良好的防光作用,呈强的协同效应;GW-540-UV-327并用体系呈弱的对抗作用。结果还表明:GW-540对531和327的光分解均有保护作用.电镜研究表明,加入GW-540后,使UV-327在聚丙烯中分散更不均匀,从而影响其效率的发挥。文中提出了两个体系的协同和对抗作用机理。     

高分子受阻胺对顺1,4-聚丁二烯溶液光敏降解过程的稳定作用

 本文研究了高分子受阻胺光稳定剂苯乙烯4-(甲基丙烯酸)-2,2,6,6-四甲基哌啶醇酯共聚物在用罗丹明6G光敏氧化降解顺1,4-聚丁二烯过程中的稳定作用。它具有淬灭单线态氧、分解过氧化氢以及捕获大分子自由基的能力,对其光稳定机理也进行了初步的讨论。     

某些高分子受阻胺对聚丙烯稳定化作用的研究

众所周知,受阻胺光稳定剂对聚烯烃有良好的光稳定效率,已引起世界的注意。然而,小分子量的受阻胺易于挥发,从而影响它的效率发挥^[1,2],为了克服这个缺点,使小分子受阻胺的高分子化是近年来受阻胺光稳定剂发展的方向,本文主要是研究三种商品化高分子受阻胺光稳定剂对聚丙烯的稳定化作用及其效率和机理。     

杯[4]芳烃-受阻胺类复合稳定剂在聚丙烯中的抗热氧稳定性能

杯芳烃;合成;杯[4]芳烃-受阻胺类复合稳定剂在聚丙烯中的抗热氧稳定性能     

Design and Synthesis of Olefin Copolymers with Tunable Amounts of Comonomers Bearing Stabilizing Functionalities

The aim of this work is to search for innovative solutions to avoid physical migration of the stabilizers from plastic films. New families of macromolecular additives bearing tuned amounts of a selected functionality were explored, in particular, novel random copolymers of ethylene with 1‐olefin co‐units bearing an efficient antioxidant and/or anti‐UV moiety covalently bonded to a mono‐ or disubstituted olefinic bond. Polyolefin blends containing the novel macromolecular additives showed higher degradation temperatures with respect to the neat matrix and its blends with 2,6‐t‐butyl‐4‐methoxyphenol (BHA). Aging tests showed that the novel antioxidants also constitute a protection against photo‐oxidation.

     

Rapid determination of oligomeric hindered amine light stabilizers in polymeric materials

Hindered amine light stabilizers are essential for the stabilization of synthetic polymers, particularly for materials used for outdoor applications. Although up to now a considerable number of studies dealing with the analytics of this class of stabilizers had been published, especially the determination of oligomeric hindered amine light stabilizers is still an analytical challenge. In the current work, a fast and simple liquid chromatographic method for the quantitative determination of oligomeric hindered amine light stabilizers is presented. A key aspect of this method is their completely different retention behavior depending on the pH, enabling a single peak elution approach by a pH gradient run. This allows a quantitation with simple UV detection independent of the actual oligomeric composition. Calibration curves within the concentration range relevant for the analysis of real polymer samples (LOQ = 70 mg/L) were constructed with R ² values above 0.99. Spiked extracts from polyolefin samples showed recovery rates between 97.3 and 102.9% for five different commercial hindered amine light stabilizers. Relative standard deviations were between 2.0 and 3.9%. Furthermore, it was demonstrated that the employed approach can be easily adapted for mass spectrometry detection.     

含抗氧化受阻胺的三聚芴有机半导体的合成及其光谱稳定性的研究

芴基电致蓝光材料低能绿光带(LEEB)的起源仍没有结论,其中芴酮诱导LEEB是重要机制之一,基于此我们提出通过引入含抗氧化的受阻胺来抑制LEEB的策略.通过复杂二芳基芴(CDAF)方式构建了一个共价键联接的含四甲基哌啶(TMP)的蓝光三聚芴有机半导体材料DF-PTMPF,并通过退火实验研究对其光谱稳定性的影响.研究结果表明DF-PTMPF的光谱稳定性有了很大提高,退火120h时的绿光指数φ为1.4(φ=IGreen/IBlue),而相同条件下的三聚芴TDHF的绿光指数φ为2.4.同时,由于受阻胺可以除掉体系中微量的氧,而DF-PTMPF在起初的氮气气氛下退火24h仍产生绿光带,这一结果暗示了聚集诱导LEEB仍不能忽视.     

UV stabilisation of powder clear coats

Powder coatings are gaining importance in exterior applications such as automotive and architectural finishes. The use of additives in powder coating formulations enhance the durability of the coating by reducing the effects of harmful UV light and providing high temperature stability during processing and curing. Customers' increased demands for better retention of aesthetical and mechanical properties has prompted the development of new additives dedicated to powder coatings. This paper presents an overview of the performance of light stabilizers used in powder coatings.     

CO2 Absorption Mechanism by the Nonaqueous Solvent Consisting of Hindered Amine 2-[(1,1-dimethylethyl)amino]ethanol and Ethylene Glycol

In this work, we studied the CO₂ absorption mechanism by nonaqueous solvent comprising hindered amine 2-[(1,1-dimethylethyl)amino]ethanol (TBAE) and ethylene glycol (EG). The NMR and FTIR results indicated that CO₂ reacted with an -OH group of EG rather than the -OH of TBAE by producing hydroxyethyl carbonate species. A possible reaction pathway was suggested, which involves two steps. In the first step, the acid–base reaction between TBAE and EG generated the anion HO-CH₂-CH₂-O-; in the second step, the O⁻ of HO-CH₂-CH₂-O⁻ attacked the C atom of CO₂, forming carbonate species.     

仲胺的合成方法新进展

介绍了近10年来合成仲胺的新方法,包括直接N-烷基化法,还原胺化法,苯并异噁唑类和2-羟基苯甲醛肟类的还原,三相反应法,保护-烷基化-去保护和不对称硼酸酯法。参考文献33篇。     

聚苯乙烯三乙醇胺树脂的合成与表征

由氯甲基聚苯乙烯与三乙醇胺反应合成了聚苯乙烯三乙醇胺树脂,通过元素分析,交换容量,溶胀性和ＩＲ对其进行表征,研究了其可能结构和某些性能。     

十六烷基胺稳定的CdSe纳米晶体的合成与表征

用CdO通过高温化学方法制备了具有高发光特性的CdSe胶体纳米晶.通过改变配体十六烷基胺在反应体系中的含量,合成了3种不同粒径的CdSe纳米晶.利用TEM、XRD和光谱等手段对合成出来的CdSe纳米晶的形貌结构和发光特性进行了表征.结果表明,随着十六烷基胺在反应体系中量的增多,CdSe纳米晶的粒径增大.通过调整十六烷基胺在反应体系中的量可以方便地控制纳米晶的尺寸.