新型树枝状受阻胺光稳定剂的设计、合成及性能评价

以二胺类化合物、丙烯酸甲酯、1,2,2,6,6-五甲基哌啶醇为主要原料, 经Michael加成、酯交换反应合成了一系列分子中含四个哌啶胺结构的新型树枝状化合物. 目标产物结构经¹H NMR, ¹³C NMR分析进行了确认. 选取其中一种结构进行抗氧化及抗老化性能测试, 结果表明其抗氧化性能优于主流抗氧剂Irganox B215及受阻胺光稳定剂Tinuvin770, Chimassorb944, Tinuvin622, 其抗老化性能优于受阻胺光稳定剂Tinuvin770.     

含空间位阻基团的超支化聚芴的合成、表征及稳定性研究

以1,3,5-间三溴苯和三(4-溴苯基)胺为支化核,引入9,10-二溴蒽和2,7-二溴-螺(芴-9,9-氧杂蒽)通过Suzuki反应与芴分别共聚,得到4种不同结构的超支化聚芴蓝光材料,对其结构及光物理性质进行了表征,根据退火前后荧光光谱的变化对其光谱热稳定性进行了研究.实验结果表明,引入超支化结构和高位阻基团,聚芴的荧光发射光谱热稳定性显著提高,绿光区发射现象几乎完全被抑制.     

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.     

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.     

N-取代烷氧基受阻胺类阻燃剂及其在聚烯烃中的应用

近年来,长期作为光稳定剂的受阻胺在性能改善过程中发现其中的N-取代烷氧基受阻胺具有优异的阻燃性能.本文对N-取代烷氧基受阻胺类阻燃剂(NORs)的结构、性能、合成、阻燃机理及其在聚烯烃中的应用进行了系统的评述.NORs主要是以2,2,6,6-四甲基哌啶衍生物在催化剂作用下与烷基自由基经过数步反应制得,其在聚烯烃中的阻燃...     

丙烯-马来酸哌啶酯共聚物的合成与表征

<正> 以2,2,6,6-四甲基哌啶为母体的衍生物作为受阻胺光稳定剂,其效率约为镍-螯合物光稳定剂的2—6倍,已引起人们的注意,但是小分子受阻胺易于挥发,从而使其光稳定作用较差。为了克服上述缺点,使受阻胺稳定剂高分子化是近年来展的趋势,本文合成了含有“丙烯”单元的高分子受阻胺光稳定剂——丙烯-马来酸哌啶酯共聚物,力求改进它与丙烯的相容性,提高光稳定效率,本文还对共聚物进行表征。     

新型水溶性共轭嵌段含糖聚合物的合成与表征

以两端溴化的聚9,9-二己基芴作为大分子引发剂, 6-O-甲基丙烯酰基-1,2∶3,4-二-O-异亚丙基-D-吡喃型半乳糖(6-O-Methacryloyl-1,2∶3,4-di-O-isopropylidene-D-galactopyranose, MaIpGa)为单体, 氯化亚铜/1,1,4,7,10,10-六甲基三乙基四胺为催化剂, 通过原子转移自由基聚合(ATRP), 合成了一种新型的具有良好光学性能的三嵌段共聚物聚甲基丙烯酸羟基保护半乳糖酯-聚芴-聚甲基丙烯酸羟基保护半乳糖酯(PMaIpGa-PF-PMaIpGa). 在酸性条件下进一步水解, 得到水溶性的聚甲基丙烯酸半乳糖酯-聚芴-聚甲基丙烯酸半乳糖酯(PMaGa-PF-PMaGa)三嵌段聚合物, 其结构和分子量(分布)通过核磁共振、红外光谱和凝胶渗透色谱(GPC)确证, 并研究了其紫外-可见和荧光光谱特性.     

1,2,2,6,6-五甲基哌啶醇光稳定作用的研究

本文研究了1,2,2,6,6-五甲基哌啶醇在异辛烷溶液中的光稳定作用。实验结果表明:五甲基哌啶醇具有和四甲基哌啶醇基本相同,而此四甲基哌啶醇氮氧自由基略优的光稳定效率;五甲基哌啶醇和四甲基哌啶醇一样,在光稳定作用过程中产生氮氧自由基,并且氮氧自由基浓度变化经历了一个最大值,但其积累的速度及达到的浓度极大值均比四甲基哌啶醇的场合为低。实验还发现,五甲基哌啶醇在光稳定过程中产生一个稳定中间产物——N-氧化-1,2,2,6,6-五甲基哌啶醇。据此,提出了五甲基哌啶醇首先转化为N-氧化物,进而转化为氮氧自由基的两步作用机理。     

1,2,2,6,6-五甲基哌啶醇对聚丙烯光稳定作用的研究

<正> 关于受阻胺类光稳定剂的稳定作用机理,是近年来光稳定研究领域中广泛探讨的课题,我们用异辛烷溶液研究了1,2,2,6,6-五甲基哌啶醇的光稳定作用,结果已在前文报道,本工作是上述研究的继续,主要研究五甲基哌啶醇对聚丙烯膜的光稳定作用。     

苯乙烯-甲基丙烯酸四甲基哌啶醇酯共聚物对聚丙烯的光照接枝研究

<正> 苯乙烯-甲基丙烯酸四甲基哌啶醇酯共聚物具有下列结构: 是高效的大分子受阻胺光稳定剂(我国商品名称为PDS)。关于它的高防护效率的原因和光防护机理研究尚少。吴世康等研究了单线态氧发生剂亚甲基蓝存在下的PDS-苯-甲醇体系的光氧化,发现PDS氮氧稳定自由基对芘的荧光猝灭还不如小分子的四甲基     

Formation of polymer-bonded nitroxyl radicals in the UV stabilization of polypropylene by a bifunctional hindered amine light stabilizer

The formation of polymer-bonded stabilizer derivatives during photooxidation of isotactic polypropylene, which contains the hindered amine light stabilizer bis(2,2,6,6-tetramethyl-4-piperidinyl) sebacate and the corresponding bisnitroxyl radical, was investigated. The photooxidized polypropylene films that contain these additives were studied by ESR, IR, and nitrogen analysis before and after exhaustive solvent extraction of the photooxidized films. ESR showed that under the conditions in use a maximum of 20% of the nitroxyl radicals formed from the hindered amine was bonded to the polymer chain. Regeneration of nitroxyl radicals from the polymer-bonded stabilizer derivatives under photooxidative conditions indicated that the stabilizer was bonded to the polymer chain by O-alkyl-substituted hydroxylamine linkages >N? O? PP.     

Synthesis of highly photostable blue-emitting 1,8-naphthalimides and their acrylonitrile copolymers

Two novel highly photostable blue-emitting 1,8-naphthalimides, containing active fragments of a hindered amine radical scavenger and an s-triazine UV absorber were designed as multifunctional additives capable of simultaneous fluorescent brightening and photostabilization of polymers. Their light absorption and fluorescence properties have been determined and discussed. The ability of the combined fluorescent brighteners to copolymerize with acrylonitrile was demonstrated by obtaining acrylonitrile copolymers with an intense blue fluorescence. Photodegradation of the new fluorophores and their influence on the photostability of the fluorescent copolymers have been studied and compared to other similar 1,8-naphthalimides, not containing either UV absorber or hindered amine fragment in their molecules as well as not containing both of them. Novel fluorophores showed the best photostability in both solution and polymer. A significant photostabilizing effect towards photodegradation of polyacrylonitrile was found.     

A study of the photolysis of a commercial hindered amine light stabilizer

The photolysis of a commercial hindered amine light stabilizer (HALS) has been studied with a range of experimental methods. The results show that the stabilizer is easily photolyzed and photolysis mechanisms are proposed.     

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。     

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。     

Separation and characterization of oligomeric hindered amine light stabilizers using high‐performance liquid chromatography with UV and quadrupole time‐of‐flight mass spectrometric detection

Hindered amine light stabilizers are an important class of stabilizers that protect synthetic polymers from degradation and thus from changing mechanical and optical properties. The current study presents an HPLC method capable of separating oligomeric hindered amine light stabilizers on a commercially available stationary phase, employing an MS‐compatible novel mobile phase. Based on the exact masses observed with Q‐TOF‐MS, a comprehensive characterization of five different types of oligomeric hindered amine light stabilizers was achieved, leading to structural information not included in the datasheets provided by the suppliers. For the different investigated hindered amine light stabilizers, a number of recurring units up to 17 and a molecular weight of 5200 g/mol were detected. Furthermore, the analysis of stabilizer extracts of processed polypropylene samples containing different types of hindered amine light stabilizers revealed significant differences in the oligomeric pattern between standards and polymer samples. Thus, changes in the analytes’ oligomeric pattern resulting from processing or aging of polymer materials can be monitored with the presented method.     

Hindered amine stabilizers investigated by the use of packed capillary temperature programmed liquid chromatography. II: Poly-(N-beta-hydroxyethyl-2,2,6,6-tetramethyl-4-hydroxypiperidyl succinate)

Three different trademark products of a hindered amine stabilizer with the IUPAC name poly-(N-beta-hydroxyethyl-2,2,6,6-tetramethyl-4-hydroxypiperidyl succinate), have been analyzed and compared to each other by the use of packed capillary temperature programmed liquid chromatography and light scattering detection. The analysis by this method has shown that the products contained approximately 50 different homologues and/or other components. The method also demonstrated its potential in purity control of products from different manufacturers.     

Study on the application of the narrow distribution and controlled molecular weight hindered amine lighter stabilizers in poly(butylene succinate)

A series of hindered amine light stabilizer (HALS) with controlled molecular weight and narrow distribution was synthesized by reversible addition-fragmentation chain transfer(RAFT) polymerization, and its application in poly (butylene succinate) (PBS) was studied through accelerated aging experiments. The effects of different molecular weight light stabilizers on the degradation of PBS were studied. The aging degree and mechanism of PBS were characterized by attenuated total reflectance Fourier transform infrared spectroscopy (ATR-FTIR), differential scanning calorimetry (DSC), scanning electron microscope (SEM) and mechanical properties testing. The extraction experiment was also carried out to study the migration of light stabilizers in PBS. Finally, the biodegradability test was conducted to study the effect of light stabilizers on biodegradation capability. The results showed that the hindered amine light stabilizer with high molecular weight can protect the PBS material to a great extent and reduce the photodegradation degree compared with the one with low molecular weight.     

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。     

Effect of thermooxidation on tinuvin 783 in LDPE films: Characterization by UV and ftir spectroscopy

The effect of thermooxidation on Tinuvin 783 which is a hindered amine light stabilizer in LDPE films has been investigated by UV and FTIR spectroscopy. Initially, a standard curve describing the variation of the concentration of Tinuvin 783 in LDPE films was plotted using the method of integration of the band area. The relation obtained was: band area = 19.6249 × [Tinuvin 783]. This equation was then applied to measure the variation of the concentration of Tinuvin 783 in the 0.2%_wt stabilized samples which have undergone thermooxidation at 90°C for 98 days. The results showed a considerable decrease in the concentration of Tinuvin 783 by 35% during the first 30 days due to probably the formation of nitroxyl radicals. After this, the concentration was observed to be unchanged and may correspond to the phase of nitroxyl radical regeneration. On the other hand, no chemical change in the stabilized LDPE films was observed by FTIR spectroscopy at 90°C during 98 days while the band characteristic of ketone groups (1720 cm⁻¹) was detected for the unstabilized samples after only 11 days. (LDPE: low density polyethylene; HALS: hindered amine light stabilizer)