吲哚啉螺噁嗪光致变色化合物的研究进展

吲哚啉螺噁嗪以相对较高的化学稳定性、光敏性和抗疲劳性,可应用在光信息记录、光致开关、传感器、油墨印刷、防伪标识、光致变色纺织物和镜片等领域,从而希望成为实用性的光致变色材料之一,近年来引起了人们的浓厚兴趣。本研究从合成方法、光致变色机理、分散介质对其影响和新型吲哚啉螺噁嗪等方面入手,对其研究现状和动向进行综述,并展望了吲哚林螺噁嗪光致变色化合物的发展前景。     

螺噁嗪的光开关特性对聚合物电致发光性能的影响

基于螺噁嗪化合物光致变色过程中的光开关特性,将光致变色螺吲哚菲并噁嗪化合物(SO)掺杂到主体电致发光材料聚[2-甲氧基-5-(2’-乙基己氧基)-对亚苯基亚乙烯](MEH-PPV)中,制成结构为ITO/PEDOT:PSS/MEH-PPV:SO/LiF/Al的发光二极管,初步探讨了光照对发光二极管性质的影响。通过光致变色反应,SO的开环成色体可充当注入载流子的陷阱而影响二极管的性质。所以,紫外光照前后MEH-PPV发光二极管的电致发光性质,包括电流、亮度、发光强度等性质,通过螺噁嗪化合物分子的光开关特性而变化。     

吲哚啉螺萘并(噁)嗪光致变色化合物的合成研究

以β-萘酚经亚硝化反应得到中间体1-亚硝基-2-萘酚;以苯肼、3-甲基-2-丁酮为原料合成得到2,3,3-三甲基-3H-吲哚,经碘甲烷季铵盐化后在碱性条件下与1-亚硝基-2-萘酚反应得到1,3,3-三甲基吲哚啉螺萘并(噁)嗪光致变色化合物.通过1H NMR、IR和元素分析确证了中间体和目标分子的结构;讨论了温度对1-亚硝基-2-萘酚合成的影响、制备吲哚季铵盐时溶剂的选择以及目标化合物的合成与光致变色机理.目标化合物的甲醇溶液经紫外光照射后由无色变为淡兰色,显示了良好的光致变色性能.     

具有光致变色功能的纤维素接枝共聚物的制备与表征

以纤维素(Cell)为原料,通过原子转移自由基聚合(ATRP)在纤维素主链上接枝了4种乙烯基单体,然后通过酯化反应接枝螺吡喃衍生物(SP-OH),得到具有光致变色功能的纤维素接枝共聚物。采用核磁谱图、红外光谱、溶解性测试、紫外吸收光谱对所得样品的结构和性能进行表征。结果表明,所制备的具有光致变色功能的纤维素接枝共聚物可以在多种有机溶剂中溶解,并且具有良好的光致变色性能及循环使用的稳定性,在紫外光照射8 min后由白色变为深紫色,并且可以保持12 h不褪色。     

吲哚啉螺吡喃的合成及其光致变色性质研究

从小分子出发通过一系列的合成步骤,最终合成了3,3-二甲基-N-乙基-6’-硝基苯并螺吡喃(SP1)、3,3-二甲基-N-乙基-5-氯-6’-硝基苯并螺吡喃(SP2)和3,3-二甲基-N-乙基-5-甲氧基-6’-硝基苯并螺吡喃(SP3)3种未见文献报道的螺吡喃。通过元素分析、红外光谱、核磁共振等手段对合成的部分中间体和目标产物的结构进行表征,并应用紫外-可见吸收光谱对其光致变色性进行了研究。     

苯并噁嗪树脂的应用研究进展

针对苯并噁嗪树脂的工业应用,综述了近年来苯并噁嗪树脂的单体合成、树脂改性及固化研究的现状.     

氧化石墨烯原位合成苯并噁嗪树脂改性材料的制备

本文采用原位合成法制备氧化石墨烯／苯并噁嗪树脂改性材料,初步对复合材料的傅里叶红外光谱、微观结构以及其性能肖氏硬度和抗压强度进行了探讨。结果表明,由苯并噁嗪树脂和氧化石墨烯／苯并噁嗪材料红外分析对比分析,氧化石墨烯有利于材料的合成和交联,而从金相显微镜对材料表面观察发现,过量的氧化石墨烯加入对复合材料的抗压强度整体性能有一定程度的影响;氧化石墨烯／苯并噁嗪树脂改性材料的肖氏硬度随氧化石墨烯含量增加而增大,且明显改善材料的硬度,在加入0．3％氧化石墨烯后,材料肖氏硬度可达到35H以上,抗压强度也有明显改善,在加入0．1％的氧化石墨烯后材料的抗压强度可以达到15．8MPa,氧化石墨烯的加入能有效的改善材料的性能。     

光致变色材料的研究与应用

变色材料在变色眼镜、光学信息存储、光分子开关等方面具有广泛的应用.主要分析了螺吡喃、俘精酸酐、二芳基乙烯以及二氧化钛、卤化银等有机和无机光致变色材料的研究现状及其变色机理,最后介绍了光致变色材料在国防以及信息存储材料等方面的应用前景.     

含羧基的聚硅氧烷类光致变色液晶的合成及性能研究

首先通过重氮化反应合成了末端为羧基的刚性基元,再经过取代、加成、酯化反应最终合成了偶氮苯类聚硅氧烷液晶.通过UV表明其具有类似小分子的光致变性.并用POM、DSC对其液晶行为进行了表征,结果表明该化合物属于近晶A型液晶,相变区间为164.68℃～251.61℃,液晶范围较宽,有望作为光控开关和新型信息存储材料.     

Microwave-assisted synthesis of photochromic spirooxazine dyes under solvent-free condition

A fast, simple and effective procedure for the synthesis of photochromic spirooxazine dyes using 1-nitroso-2-naphthol and 2-methylene indolenine derivatives has been developed under solvent-free microwave irradiation condition.     

含偶氮苯侧链的新型三阶非线性聚炔材料的制备及性能

我们以中等产率成功的合成出一种含偶氮苯功能基团的、可溶解的、立体规整的、中等分子量的聚炔高分子.采用五步法合成了新颖的偶氮苯乙炔单体,2-[N-甲基-N-4-[(4-乙炔苯基)偶氮苯基]氨基]乙基丁酸酯.使用[Rh(nbd)Cl]2-Et3N将单体进行了聚合.采用FT-IR,UV-vis,GPC和NMR等对得到的聚炔高分子分子结构进行了表征.在8ns脉宽波长532 nm激光下采用Z-扫描技术对聚合物的溶液进行了非线性光学性能的测试.     

含噁二唑侧链的新型三阶非线性聚炔材料的制备及性能

使用[Rh(nbd)Cl]2-Et3N作催化剂合成了一种新的含噁二唑功能基团可溶解的聚炔高分子.采用FT-IR、UV-vis、GPC、TGA 和NMR等对得到的聚炔高分子的分子结构进行了表征,使用4.5ns脉宽波长532nm激光,采用Z扫描技术测试了聚合物的非线性光学性能.     

Synthesis and characterization of novel liquid crystalline polymers containing cholesteryl pendant groups

In order to investigate the chiral effect of cholesteryl pendant groups on the induction of the cholesteric phase, a new cholesteryl-containing liquid crystalline monomer was synthesized and copolymerized with an achiral comonomer in various molar ratios. The layer-like arrangement of the smectic mesophase with different monomeric compositions of copolymers was investigated using an X-ray diffraction analysis. The cholesteric liquid phase was induced by the chiral segments; the dependence of the reciprocal central reflection wavelength on the mole fraction of the chiral monomer for copolymers was investigated. This paper demonstrates the effect of chiral pendant groups on the induction of the cholesteric phase and layered molecular arrangement of side-chain liquid crystalline polymers.     

Synthesis and properties of novel chiral side-chain liquid crystalline polysiloxanes containing different chiral pendant groups

Two novel chiral liquid crystalline monomers, and a series of their corresponding chiral side-chain polymers (P₁–P₇) based on poly(methylhydrogeno)siloxane have been prepared. The chemical structures and liquid crystalline properties of the synthesized monomers and polymers have been investigated using various experimental techniques. Thermal analysis shows that all polymers have wide mesophase temperature ranges with a high thermal stability. With the increase of M₂ molar ratio in the polymer systems, the isotropic phase transition and glass transition temperatures of all polymers increase, and the temperature ranges of N* phase and mesophase become broad. The effect of cholesteryl mesogens on mesophase behaviors, optical properties, and molecular arrangement of LC polysiloxanes and their advanced applications have also been discussed. For homopolymer P₁, it shows a single S_A phase. With increasing the content of M₂ in the polymer systems, P₂ and P₃ reveal a S_A–N* phase transition when they are heated, and P₄–P₇ reveal a N* phase. For N* phase polymers P₄–P₇, the reflection wavelengths exhibit blue shift, suggesting that the pitch decreases with a decrease in the amount of the smectic domains induced by the M₁. The reflection wavelengths of P₄–P₇ are almost across the entire visible region when they are heated, which offer stremendous potential for various optical applications. For P₂ and P₃, the reflection wavelengths show a very steep change around the temperature of the S_A–N* phase transition, which can be used as thermally sensitive liquid crystal devices requiring fast response, such as sensors, and thermally induced tuning.     

Synthesis and optical properties of photochromic perinaphthothioindigo

(1,2-naphtho)(1,8-naphtho)thioindigo (PNT) has been synthesized following a simple Friedel–Crafts route and its photochemical properties in toluene and polymethylmethacrylate (PMMA) have been characterized. PNT is a photochromic molecule capable of reversible photoisomerization between a yellow form (cis-PNT, λ_max = 484 nm) and a purple form (trans-PNT, λ_max = 595 nm). The stable purple form converts to the yellow form with a trans-PNT to cis-PNT conversion quantum yield of 0.027 in toluene and 0.062 in PMMA. The unstable yellow form exhibits a cis-PNT to trans-PNT quantum efficiency of conversion of 0.27–0.85 in toluene and 0.17–0.68 PMMA, with highest conversion efficiency occurring in the vicinity of its λ_max of 484 nm. trans-PNT has a strong fluorescence quantum yield, 0.14 (toluene) and 0.16 (PMMA). For samples prepared photochemically in the cis-PNT form, slow thermal relaxation to the trans form occurs in the dark, with a half life of about 17 h in toluene (25 °C) and even slower, 168 h, in PMMA. The property of photoswitching between fluorescent and non-fluorescent forms makes this material a candidate for many applications in imaging and data storage.     

Synthesis and optical properties of photochromic perinaphthothioindigo

(1,2-naphtho)(1,8-naphtho)thioindigo (PNT) has been synthesized following a simple Friedel–Crafts route and its photochemical properties in toluene and polymethylmethacrylate (PMMA) have been characterized. PNT is a photochromic molecule capable of reversible photoisomerization between a yellow form (cis-PNT, λ_max = 484 nm) and a purple form (trans-PNT, λ_max = 595 nm). The stable purple form converts to the yellow form with a trans-PNT to cis-PNT conversion quantum yield of 0.027 in toluene and 0.062 in PMMA. The unstable yellow form exhibits a cis-PNT to trans-PNT quantum efficiency of conversion of 0.27–0.85 in toluene and 0.17–0.68 PMMA, with highest conversion efficiency occurring in the vicinity of its λ_max of 484 nm. trans-PNT has a strong fluorescence quantum yield, 0.14 (toluene) and 0.16 (PMMA). For samples prepared photochemically in the cis-PNT form, slow thermal relaxation to the trans form occurs in the dark, with a half life of about 17 h in toluene (25 °C) and even slower, 168 h, in PMMA. The property of photoswitching between fluorescent and non-fluorescent forms makes this material a candidate for many applications in imaging and data storage.     

氰基联苯乙烯类双光子吸收材料的合成

合成了一种新型双光子吸收材料氰基联苯乙烯类化合物,通过元素分析、电喷雾质谱、1H NMR和红外对其进行表征.测试了紫外吸收光谱、单光子荧光光谱、单光子荧光寿命和双光子荧光光谱.其双光子吸收截面为1.32×10-48cm4·s·photon-1,是潜在应用前景的双光子吸收材料.