Preparation of a spirooxazine grafted PMMA and its photochromic properties

A novel spirooxazine (SO) compound was designed and synthesized. Macromolecular materials, called SO-g-hPMMAs (where the g means grafting and the h means partial hydrolysis), were prepared using PMMA (polymethylmethacrylate) with different degrees of hydrolysis. SO-g-5%hPMMA was prepared by reacting SO-containing active C-Br bonds with 5% partially hydrolyzed PMMA. The SO was characterized using ¹H NMR and infrared. Beyond that, photochromic properties were studied in detail. We discuss the effects of hydrochloric acids and hPMMAs of different hydrolysis degrees on photochromic properties of SO-g-hPMMA. Additionally, mechanical properties of the material were studied. Results indicate that the colored ring-opening form (PMC) of SO-g-hPMMA exhibits a good performance in terms of thermal stability, in contrast to the homologous SO. Experiments additionally demonstrate that hydrochloric acid improves the PMC’s thermal stability. SO-g-9%hPMMA demonstrated a good performance of photochromic properties compared to those with different degrees of hydrolysis.     

ORMOCER Coatings Based on Titanium and Poly(tetraethylene glycol malonate)

Organically modified hybrid ceramic oxide coatings based on titanium and poly(tetraethylene glycol malonate) (PTEGM) have been prepared by sol-gel methods and the structure characterized by FT-IR spectroscopy and X-ray photoelectron spectroscopy. Results indicate that malonate units (TEGM) in PTEGM form a co-ordination bond with titanium, enabling titania to be homogeneously distributed in the polymer matrix. For molar ratios [TEGM] : [TIP] = 1 and 4 maximum crack-free thicknesses of 1.2 and 15 m, respectively were achieved in a single dip. Ionic conductivity measurements were performed on coatings having molar ratios [TEGM] : [Ti] : [Li+] = 5 : 1.25 : 1, with lithium perchlorate as the electrolyte, giving a relatively high solid-state ionic conductivity of ca. 10–5 S cm–1 at room temperature.     

Synthesis and photochromic properties of WO_3 powder induced by oxalic acid

Tungsten trioxide powder with the novel morphology was prepared via the hydrothermal method with oxalic acid as the organic inducer, the structure and shape of which were detected by X-ray diffraction (XRD), scanning electron microscopy (SEM) and BET. Furthermore, photochromic properties of the as-prepared powder samples were tested by an ultraviolet-visible spectrophotometer combined with a color difference meter. The corresponding results indicated that the induced product was still hexagonal WO3, made up...     

A New Approach to Characterization of Barrier Properties of ORMOCER Protective Coatings

The Radiometric Emanation Method (REM) was used for the characterization of barrier properties of protective coatings. Radon diffusion parameters of the hardened protective layers prepared from ORMOCER lacquers of varying compositions were examined. The differences in the barrier properties of non weathered and weathered ORMOCER coatings, as well as of INCRALAC coatings, were compared. REM is recommended for the characterization of barrier properties of protective coatings submitted to weathering at varying conditions and time.     

Synthesis and properties of a novel photochromic luminophore

A photochemically bifunctional compound was obtained. Its molecule includes the spironaphthoxazine and dansylamino fragments. This compound exhibits both photochromic and luminescent properties. Its spectroscopic characteristics were studied in different solvents. The electronic systems of two constituent fragments do not interact with each other. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 12, pp. 2802–2805, December, 2005.     

光致变色冠醚部花菁染料的合成及其逆光致变色性

作者用含冠醚结构单元的2-甲基-苯并噻唑季铵盐与取代水物醛缩合得到了五个光致变色冠醚部化菁化合物。这些新的冠醚化合物具有逆光致变色性质, 较稳定的结构是开环部花菁式。     

Synthesis and photochromic properties of spiro (benzindoline-naphthoxazines)

A new photochromic compound belonging to the class of spiro(indoline-naphthoxazines) was synthesized. Nitration of this compound was carried out and the structures of two photochromic nitro-substituted products were determined. The photochromic properties of the products were studied in solvents of different polarity.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 4, pp. 732–736, April, 1995.     

冠醚螺吡喃化合物的合成和光致变色性质

合成了四个新的6位带不同取代基的含冠醚结构单元吲哚啉螺苯并吡喃化合物(5a-5d),研究了其光致变色性质和离子诱导光致变色作用及取代基的影响。结果表明冠醚能稳定螺吡喃开环形式,碱金属离子对冠醚螺吡喃的生色有诱导作用;6位为吸电子基团时,螺吡喃开环形式的稳定性增加,而6位为推电子基团时,螺吡喃开环形式的稳定性降低。另外,就稳定螺吡喃开环体的作用来说,吲哚啉环上的取代基效应和苯并吡喃环上的正好相反。     

光致变色多孔聚苯乙烯功能微球的制备和性能

以甲苯/庚烷为致孔剂,利用分散聚合技术制备了多孔交联聚苯乙烯微球.研究了聚合单体、引发剂、稳定剂、交联剂等对微球平均粒径的影响,并初步评价了其在常温常压下吸附光致变色材料后的光致变色性能.结果表明,在最佳条件下制得的多孔聚合物微球平均粒径为1 μm;吸附光致变色材料后,其在紫外或日光照射下具有快速可逆的光致变色功能.利...     

Preparation and photochromic properties of oligomeric poly(dimethylsiloxane) with the spiropyran or spirooxazine moiety in the side chain

Spirobenzopyran 1 , with the 3-(diethoxymethylsilyl)-propyl group at the N atom, was synthesized. The condensation reaction of the spiropyran 1 and diethoxydimethylsilane gave oligomeric poly(dimethylsiloxane) with the spiropyran moiety in the side chain. The oligomer was photochromic; its colour changed from colorless to purple-red on uv irradiation and the color faded on visible irradiation or on standing in the dark. The half-decay time of the thermal decoloration was about twice that of monomeric spiropyran dissolved in the dimethylsiloxane oligomer. Photochromic poly(dimethylsiloxane) with the spirooxazine moiety in the side chain was also prepared.     

两个紫精-多酸杂化材料的合成、结构及其光致变色和光催化性质

分别利用1,1''-二甲基-4,4''-联吡啶(甲基紫精,MV)二氯化物和1,1''-二乙基-4,4''-联吡啶(乙基紫精,EV)二溴化物的阳离子作为电子受体,富电子的杂多酸阴离子作为电子给体,合成了 2 个新的紫精-多酸杂化晶态材料：(MV)₂[HPW^Ⅴ₂W^Ⅵ₁₀O₄₀]·2H₂O (1)和(EV)₂[Mo₈O₂₆] (2),并解析了其单晶结构,在化合物 1和 2中,阴、阳离子间均存在氢键相互作用。2具有光致变色性能,光响应时间为1 min以内。通过固体漫反射、电子顺磁共振和理论计算等手段,探究了2的光致变色机理。1和2对光降解有机染料(亚甲蓝、盐酸副玫瑰苯胺和罗丹明6G)均具有一定的催化性能。     

两个紫精-多酸杂化材料的合成、结构及其光致变色和光催化性质

分别利用1,1''-二甲基-4,4''-联吡啶(甲基紫精,MV)二氯化物和1,1''-二乙基-4,4''-联吡啶(乙基紫精,EV)二溴化物的阳离子作为电子受体,富电子的杂多酸阴离子作为电子给体,合成了 2 个新的紫精-多酸杂化晶态材料：(MV)₂[HPW^Ⅴ₂W^Ⅵ₁₀O₄₀]₂·2H₂O (1)和(EV)₂[Mo₈O₂₆] (2),并解析了其单晶结构,在化合物 1和 2中,阴、阳离子间均存在氢键相互作用。2具有光致变色性能,光响应时间为1 min以内。通过固体漫反射、电子顺磁共振和理论计算等手段,探究了2的光致变色机理。1和2对光降解有机染料(亚甲蓝、盐酸对甲苯胺和罗丹明6G)均具有一定的催化性能。     

Synthesis, structures, and photochromic properties of N-aryl-3-indolylfulgides

New 3-indolylfulgides, viz., 3-[1-(1-aryl-5-methoxy-2-methyl-1H-indol-3-yl)ethylidene]-4-(1-methylethylidene)tetrahydro-2,5-furandiones, were synthesized. These compounds were obtained as E-isomers, as demonstrated by X-ray diffraction, electronic spectroscopy, and ¹H NMR spectroscopy. Fulgides exhibit photochromic properties in solution. The cyclic dihydrocarbazole photoisomers of indolylfulgides show fluorescence properties and are characterized by high thermal stability. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 7, pp. 1417–1423, July, 2008.     

三种苯并噻吩缩氨基硫脲类化合物的固态光致变色性能研究

本文通过结构修饰,在苯并噻吩缩氨基硫脲侧链的同一位点引入具有不同共轭性的取代基(烯丙基、环已基和苯基),合成了三种具有固态光致变色性能的1-(苯并噻吩-2亚甲基)-4-取代基-氨基硫脲类化合物,并对化合物的结构进行了表征,同时利用紫外-可见吸收光谱和光致变色动力学分析了三种化合物的光致变色性能、热力学变化和抗疲劳性,探...     

Structure and photochromic properties of molybdenumphosphoric acid/TiO_2 composite films

TiO_2 sol-gel composite films with dropping molybdenumphosphoric acid(PMoA) have been prepared by sol-gel method.The structure and constitute of composite thin films were studied with Fourier transforms infrared spectroscopy(FT-IR),atomic force microscopy(AFM),and X-ray diffraction(XRD) patterns,respectively.The photochromic behavior and mechanism of composite thin films were inves-tigated with ultraviolet-visible spectra(UV-vis) and electron spin resonance(ESR).FT-IR results showed that the Keggin geometry...     

Synthesis and photochromic properties of WO<Subscript>3</Subscript> powder induced by oxalic acid

Tungsten trioxide powder with the novel morphology was prepared via the hydrothermal method with oxalic acid as the organic inducer, the structure and shape of which were detected by X-ray diffraction (XRD), scanning electron microscopy (SEM) and BET. Furthermore, photochromic properties of the as-prepared powder samples were tested by an ultraviolet-visible spectrophotometer combined with a color difference meter. The corresponding results indicated that the induced product was still hexagonal WO₃, made up of regularly spindle particles with 200–300 nm in length and 30–50 nm in width. The ratio of the length and width was from 4 to 10. Moreover, the special morphology improved its absorptive capacity to the excitation light source, resulting in its high photochromic properties. Supported by the National Natural Science Foundation of China (Grant No. 50702052) and the Hubei Province Key Laboratory of Macromolecular Material     

Synthesis of polymerizable photochromic spironaphthoxazines

Hydrogenatjon of 8-nitrospironaphthoxazine (1) resulted in the corresponding amine (2). Acylation of compound 2 yielded the N-methacryloyl derivative (3). Radical polymerization of the latter resulted in its copolymers with styrene, which possess photochromic properties.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 5, pp. 1243–1245, May, 1996.     

Synthesis,photochromic mechanism and properties of a novel biindenylidenedione compound containing ferrocene units

A novel biindenylidenedione compound, [2,2′‐bi‐1H‐indene]‐3,3′‐bis [(4‐oxo‐4‐ferrocenylbutanoyloxy)propyl]‐3,3′‐ dihydroxy‐1,1′‐dione was synthesized and characterized fully by ¹H NMR, IR, MS and elemental analysis. The photochromic and photo‐induced radical properties were investigated by means of UV–vis and electron spin resonance spectroscopy, respectively. The results show that the title compound simultaneously exhibits photochromism in the solid state as well as generating stable free radicals under irradiation with 330 nm light. This fact provides evidence for the photochromic mechanism of this kind of compounds. Copyright © 2008 John Wiley & Sons, Ltd.