螺噁嗪化合物在丙烯酸聚氨酯清漆膜中的光致变色性能

制备了含有螺噁嗪(SO)化合物的紫外光固化丙烯酸聚氨酯清漆(UV-PUA)膜, 研究了SO在该清漆中的光致变色性能, 并与其在聚甲基丙烯酸甲酯(PMMA)中的光致变色性能进行了比较. 结果发现, 紫外光固化螺噁嗪丙烯酸聚氨酯清漆(UV-SO-PUA)膜在紫外光固化过程中逐渐由无色变为蓝色和紫色, 撤去紫外光源, 漆膜退色至粉色, 且固化后的漆膜在粉色和紫色之间可逆变化; 而SO-PMMA膜在无色和蓝色之间可逆变化. 紫外光激发的UV-SO-PUA膜的紫外-可见吸收光谱可见光区出现了明显的双重吸收峰(520和600 nm), 而在PMMA中仅出现单峰. SO开环体在UV-PUA 中室温稳定性优于其在ＰＭＭＡ中的稳定性. SO在UV-PUA膜中的抗疲劳性能与其在PMMA中相比显著提高, 紫外光照射16 h, UV-SO-PUA漆膜未出现疲劳现象. SO在UV-PUA膜中表现出了优良的光致变色行为.     

Factors Influencing Photochromism of Spiro-Compounds Within Polymeric Matrices

Abstract

Photochromic polymeric materials have been commercialized in ophthalmic lenses, however, there are many other potential uses for this technology. The photochromic transitions are extremely sensitive to environmental conditions, thus offering the potential for modifying the kinetics to suit different applications. There are a significant number of photochromic molecular families, with different characteristics. The spiro-compounds, both spirooxazines and spiropyrans, have received the most attention as they have good coloration properties and spirooxazines also display good fatigue resistance. Consequently this review focuses on the inclusion of these compounds into polymer matrices. In addition we discuss decoloration and coloration behaviors, solvatochromism, mechanism of fatigue, and unusual synthetic approaches.     

乙烯基噻吩共轭螺噁嗪化合物的密度泛函理论研究

采用密度泛函理论(DFT)方法, 在B3LYP/6-31G^* 水平上对乙烯基噻吩共轭螺噁嗪化合物 SO-SO3 的几何构型、电子结构、前线分子轨道等进行了理论研究, 计算结果表明: SO-SO3的开环过程会使得开环体的左右两个部分键长均等化, 导致共轭体系变大, 能隙明显减小; 乙烯基噻吩基团共轭接入螺噁嗪母体后, 导致体系的共轭作用变大, 在激发态下电子流动增强, 形成由乙烯基噻吩向萘并噁嗪的有效电荷转移与能量转移; 结合前线分子轨道成分分析乙烯基噻吩单元在最高占据分子轨道(HOMO)和最低未占据分子轨道(LUMO)中的轨道贡献率明显增加. 含时密度泛函理论(TD-DFT)计算的电子吸收光谱结果显示: 当接入的乙烯基噻吩单元达到2-3个时, 影响SO2和SO3开环的最低能量激发态变为第一激发单重态S₁, 并且均源自电子从HOMO至LUMO的跃迁且为π-π^*跃迁; 其最大吸收波长λ_max 达到466-540 nm, 且红移十分明显, 其对应开环体O-SO2与O-SO3的λ_max 达到605和647 nm.     

与二茂铁酰基相连的螺噁嗪的合成、结构及性质

在二环已基碳二亚胺(DCC)存在下, 将9′-羟基螺噁嗪与二茂铁甲酸进行酯化缩合, 合成了一种与二茂铁酰基相连的螺噁嗪衍生物2, 用核磁共振氢谱、碳谱、红外光谱、高分辨质谱和X射线单晶衍射对其结构进行了表征. 化合物2在几种有机溶剂中都表现出了良好的光致变色性质; 通过实验证明了在无冰水浴冷却条件下, 用高压汞灯照射时化合物2在二氯甲烷中表现出的特殊变色性是酸致变色的结果; 同时还研究了化合物2在固体PMMA薄膜中的光致变色性质. 在高压汞灯照射下,化合物2在二氯甲烷溶液中显示了良好的荧光性. 循环伏安法测定结果表明化合物2具有良好的氧化还原可逆性.     

光致变色化合物的研究——1，3，3—三甲基—6‘—（1—哌啶基）—螺[2H—吲哚—2，3’—[3H]吡啶[3,2—f][1,4]苯并恶嗪]的合成

螺嗪类化合物是在螺吡喃基础上发展起来的一类新的光致变色化合物 ,与螺吡喃相比 ,具有化学性质稳定 ,光响应快 ,抗疲劳性好等优点 ,在光信息记录、非银感成像、非线性光电器件、光过滤器、防伪以及装饰等领域具有很大的应用潜力[1] 。吲哚啉螺嗪的基本结构及光致色变过程可表示为 :　　其中Ｘ为 (杂 )芳环与苯环相并 ,可带有取代基。螺嗪ＳＰ(Ｓｐｉｒｏｏｘａｚｉｎｅ)经光λ1激发后 ,开环变成具有大共轭体系的开环体ＰＭＣ(Ｐｈｏｔｏｍｅｒｏｃｙａ ｎｉｅｓ) ,从而使其光吸收红移 ,停止激发后 ,ＰＭＣ可通过λ2 或以热作用方式回…     

含螺噁嗪光致变色薄膜的全光开关特性

采用旋涂法和滴涂法制备了含螺噁嗪光致变色分子的不同基质薄膜,并将其应用于全光开关实验中.分别对含有螺噁嗪的聚甲基丙烯酸甲酯薄膜和二氧化硅薄膜的光致变色特性进行了吸收光谱的比对研究,结果表明:螺噁嗪/聚甲基丙烯酸甲酯薄膜经过多个开关周期后透射信号强度明显衰减;螺噁嗪/二氧化硅薄膜透射信号强度保持不变,具有更为优异的光学可逆性,更适合于作全光开关.在全息光开关实验中,选用螺噁嗪/二氧化硅薄膜,采用光擦除和热擦除两种方法研究了它的输出光信号衰减动力学特性,发现光擦除具有更短的响应时间.基于光擦除法研究激发光功率为5mW、10mW、25mW时的光开关特性,发现当激发光为10mW时,光栅对比度、衍射信号强度和开关对比度等特性最佳.     

Synthesis and Photochromism of Novel Spiro(indoline-2,3'-naphtho[2,1-b][1,4]oxazine)

A series of novel spirooxazine(SPO) derivatives containing nitrogen heterocycles was synthesized and characterized by ¹H NMR spectra, Fourier transform infrared(FTIR) spectra, mass spectra(MS) and elemental analysis, and their photochromic behaviors were fully investigated in solvents and polymer media. In solvents, they displayed excellent photochromism properties such as high photochromic response and fast thermal bleaching rate. Especially, compounds 1 and 4 exhibited strong fluorescence intensities in dichloromethane solution. It was additionally found that compound 4 showed high fatigue resistence in poly(methyl methacrylate)(PMMA) film, and the thermal decay curves were fitted with biexponential function in PMMA film.     

新型有机光致变色材料螺嗪的结构确证

采用^1H NMR谱、^13C NMR谱、DEPT（θ=3π/4）谱、红外吸收光谱、质谱等仪器分析手段确证了4种新合成的有机光致变色材料螺E嗪化合物的结构,并对化合物的^13C NMR谱化学位移和质谱碎片进行了归属和确认。     

Synthesis and properties of 1,3,3-trimethylspiro[indoline-2,3′-naphtho[2,1-b][1,4]oxazin]-6′-amine, a novel, red colouring photochromic spirooxazine

The synthesis and photochromic properties of 1,3,3-trimethylspiro[indoline-2,3′-naphtho[2,1-b][1,4]oxazin]-6′-amine, a novel red-colouring photochromic spirooxazine and derivatives is reported. The synthesis proceeds via an unusual one-pot transamination, oxime formation, N-O bond cleavage, spirooxazine formation process.     

Photochromic properties of 1,3,3-trimethylspiro[indoline-2,3′-[3H]naphtho[2,1-b][1,4]oxazine] doped in PMMA and epoxy resin thin films

Irradiation of colorless 1,3,3-trimethylspiro[indoline-2,3′-[3H]naphtho[2,1-b][1,4]oxazine] SO doped in PMMA and epoxy resin with UV light (at 366 nm) results in the formation of an intensely colored zwitterionic photomerocyanine PMC. The reverse reaction was photochemically induced by irradiation with white light. Photocoloration and photobleaching reactions follow a first-order rate equation. It was found that photocoloration rate constant of SO in PMMA film is greater than that in epoxy resin. On the other hand, the photobleaching rate constant is almost identical in both matrices. Spirooxazine doped in epoxy resin shows much better fatigue resistance than that doped in PMMA.