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1.
Sung‐Ho Jin Sung‐Hyun Kim Yeong‐Soon Gal 《Journal of polymer science. Part A, Polymer chemistry》2001,39(22):4025-4034
New crosslinkable polymers with a nonlinear optical (NLO) active chromophore as a pendant group were synthesized by condensation chain polymerization via palladium‐catalyzed carbon–carbon coupling reactions. The polymerization yields were almost quantitative between the diiodobenzene (DIB) and diethyldipropargyl malonate (DEDPM) or 4‐(dimethylamino)‐4′‐(6‐dipropargylacetoxypropylsulfonyl)stilbene (DASS‐6) monomers. To improve the molecular weight and mechanical properties of the NLO active polymer, we carried out the copolymerization with DIB and DASS‐6 with various feed ratios of DEDPM. The resulting polymers were soluble in organic solvents and spun‐cast onto indium tin oxide‐coated glass substrates to make thin films. The molecular structures of the resulting polymers were characterized with various instrumental methods to confirm the carbon–carbon coupling reactions between the DIB and diacetylene monomers. The absorption of the ultraviolet–visible spectrum of the resulting polymers was drastically reduced after thermal curing at 160 °C because of the crosslinking of the reactive acetylene group in the polymer backbone. The electrooptic coefficient (r33) measured at 1.3 μm ranged from 7 to 15 pm/V. © 2001 John Wiley & Sons, Inc. J Polym Sci Part A: Polym Chem 39: 4025–4034, 2001 相似文献
2.
Katsumi Inomata Shigeo Kawasaki Atsushi Kameyama Tadatomi Nishikubo 《Journal of polymer science. Part A, Polymer chemistry》2001,39(4):530-538
Novel multifunctional photopolymers with both pendant epoxy groups and phenacyl ester groups were synthesized by the one‐pot method for the reaction of poly(methacrylic acid) with epibromohydrin; this was followed by a reaction with phenacylbromide with 1,8‐diazabicyclo‐[5.4.0]undecene‐7 as a condensation reagent. These esterification reactions proceeded smoothly and quantitatively under mild conditions. Moreover, the photochemical reactions of the resulting polymers were evaluated by UV and IR spectroscopy. The pendant phenacyl ester groups were photocleaved to give corresponding carboxyl groups, and then the produced carboxyl groups reacted with pendant epoxy groups. Furthermore, the baking process promoted a crosslinking reaction because of the addition reaction of epoxy groups with carboxyl groups after irradiation. It was also proven that the photochemical reactivity of the resulting polymers was affected by the structure of the phenacyl ester group. © 2001 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 39: 530–538, 2001 相似文献
3.
Tadatomi Nishikubo Atsushi Kameyama Katsuhiko Kishi Yasushi Mochizuki 《Journal of polymer science. Part A, Polymer chemistry》1994,32(14):2765-2773
New photoresponsive polymers 1–4 containing pendant norbornadiene (NBD) moieties with N,N-disubstituted amide groups were synthesized with 97, 98, 92, and 94% conversions by the substitution reaction of poly (p-chloromethyl) styrene] with potassium salts of 3piperidyloxo-2,5-NBD-2-carboxylic acid, 3-(NN-dipropylcarbamoyl) -2,5-NBD-2-carboxylic acid, 3-(N-methyl-N-phenylcarbamoyl)-2,5-NBD-2-carboxylic acid, and 3-(N,N-dipheylcarbmoyl)-2,5-NBD-2-carboxylic acid, respectively, using tetrabutylammonium bromide as a phase transfer catalyst for all. Polymers 1–4 with N,N-disubstituted amide groups on the NBD moieties were sensitized by adding appropriate photosensitizers such as Michler's ketone and 4- (N,N-dimethylamino) benzophenone in the film state, although the reactivities of the polymers without photosensitizer were lower than that of our previously reported polymer 5 containing pendant 3- (N-phenylcarbamoyl) -2,5-NBD-2-carboxylate moiety. It was also found that the photo-irradiated retaining polymers 1–4 containing the corresponding QC moieties can be stored about 80–86 kJ/mol of their thermal energy. © 1994 John Wiley & Sons, Inc. 相似文献
4.
Ahmed Oueslati Hatem Ben Romdhane Vincent Martin Fréderic Schiets Régis Mercier Refaât Chaâbouni 《Journal of polymer science. Part A, Polymer chemistry》2011,49(9):1988-1998
A novel pentamethylated norbornadiene (NBD) based dianhydride, α,α′‐bis‐(3,4,5,6,7‐pentamethylcyclopenta‐2,4‐dienyl)meta‐xylene‐1,2‐dianhydride (3), was prepared from α,α′‐bis‐(pentamethylcyclopentadienyl)meta‐xylene (1) and acetylene dicarboxylic acid. The bis‐adduct formed via Diels–Alder reaction afforded tetra‐acid (2), which was chemically cyclodehydrated to lead the targeted dianhydride (3). New polyimides containing NBD moieties in the main chain were prepared from the dianhydride monomer (3) and various aromatic diamines. The chemical structure of the polymers was confirmed by both 1H and 13C NMR analysis. Their Molecular weights were also measured by SEC. All of these polyimides are soluble at room temperature in common organic solvents, such as chloroform, dichloromethane, THF, DMSO, DMF, and NMP, and show good thermal stabilities. The photochemical isomerization of the NBD into quadricyclane (QC) was investigated by UV/vis spectrophotometry from polymer films using visible sunlight as irradiation source. It was found that the kinetic rate of the conversion NBD‐QC which proceeded smoothly is a first kinetic order. The stored energies released by the transformation of QC groups into NBD ones of the irradiated polymer films were also evaluated by DSC measurement and were found to be around 90 kJ mol?1. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011 相似文献
5.
Naoyuki Kawashima Atsushi Kameyama Tadatomi Nishikubo Takabumi Nagai 《Journal of polymer science. Part A, Polymer chemistry》2001,39(10):1764-1773
The donor–acceptor-type norbornadiene (D–A NBD) 1,4,5,6-tetramethyl-3-phenyl-2,5-NBD-2-carboxylic acid was prepared by the Diels–Alder reaction of methyl 3-phenylprop-2-ynoate with 1,2,3,4-tetramethyl-1,3-cyclopentadiene. 1,4,5,6,7-Pentamethyl-3-phenyl-2,5-NBD-2-carboxylic acid was also synthesized in the same way. Styrene-type polymers with pendant D–A NBD moieties were prepared with a 100% degree of substitution (DS) by the reaction of D–A NBD carboxylic acids with poly[(p-chloromethyl)styrene] with 1,8-diazabicyclo[5.4.0]undecene-7 in dimethyl sulfoxide at 70 °C for 6 h. In the reaction of D–A NBD carboxylic acids with poly(2-chloroethyl vinyl ether), the DSs were about 60%. The photochemical valence isomerizations of all the NBD polymers proceeded smoothly with UV irradiation in tetrahydrofuran solutions and in the film state. In addition, the rate of the photochemical reaction of the NBD polymers increased efficiently by the addition of 4,4′-bis(diethylamino)benzophenone as a photosensitizer in a film state. The stored thermal energy of the irradiated polymers was also evaluated by differential scanning calorimetry to be 55–74 kJ/mol. © 2001 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 39: 1764–1773, 2001 相似文献
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Gürsoy Süleyman Koçak Makbule Cihan Ali Gül Ahmet Bekaroğlu Özer 《Transition Metal Chemistry》2000,25(4):474-477
A new soluble vic-dioxime ligand namely 1,4-bis(2′-hydroxyethyl)-2,3-bis(hydroxyimino)-5,6-diphenylpiperazine, (LH2) containing optically active centers has been prepared as a mixture of isomers from (CNO)2 and N,N-bis(2-hydroxyethyl)stilbendiamine (1) which has been made by the reduction of the condensation of the product of benzaldehyde and 2-aminoethanol in the presence
of aluminum amalgam. N,N-coordinated planar metal complexes of this ligand have been synthesized with NiII, CuII, CoII, PdII and UVIO2. Oxidation of (LH)2Co in the presence of a base, such as pyridine, leads to an octahedral complex (LH)2CopyCl containing pyridine and chloride as axial ligands in addition to vic-dioxime ligands. The structures of the ligand and its complexes are proposed on the basis of elemental analysis, 1H-n.m.r., mass, i.r. and u.v.–vis. spectral data.
This revised version was published online in June 2006 with corrections to the Cover Date. 相似文献
8.
A novel molecule containing electron-rich carbazole and electron-deficient pyrimidine moieties exhibits useful and intriguing physical properties, including promising reversible redox behavior that gives rise to electrogenerated chemiluminescence (ECL). 相似文献
9.
The electrochemical properties of protoporphyrin IX zinc(II) (ZnPP) films on indium-tin oxide (ITO) substrate have been studied for three types of films with different arrangements, which were an adsorbed film of ZnPP and LB films of ZnPP and its hybrid with hexadecyltrimethylammonium bromide. Cyclic voltammetry (CV) measurement showed that, as the adsorbed amount of ZnPP increases, an irreversible oxidation peak of ZnPP film is intensified. This reveals that electrochemical properties depend on the adsorbed amount rather than the orientation of porphyrin molecules. It was also supported from CV measurement and ultraviolet-visible absorption spectroscopy that porphyrins adsorbed on ITO substrate were desorbed after the single scan of potential. Additionally, photoresponse of these ZnPP films was investigated by photocurrent measurement. The photocurrent generation is due to carboxylic acid moieties but not ZnPP macrocycles. 相似文献
10.
David Ayala Angel E. Lozano Javier De Abajo Jos G. De La Campa 《Journal of polymer science. Part A, Polymer chemistry》1999,37(6):805-814
New dianhydrides containing t‐butyl and phenyl pendant groups have been synthesized and used as monomers, together with commercial diamines, to prepare novel polyimides. The influence of the chemical structure of the monomers on their reactivity has been studied by quantum semiempirical methods. The polyimides have been characterized by FTIR and by NMR in the case of soluble polymers. The presence of pendant groups and the method used to imidize polyimide precursors greatly affected polymer properties such as solubility, glass transition temperature, thermal stability, and mechanical properties. As a rule, the novel polyimides showed better solubility in organic solvents than the parent polyimides. Glass transition temperatures in the range 250–270°C and decomposition temperatures over 520°C were observed for the set of current polymers. Tensile strengths up to 135 MPa and mechanical moduli up to 3.0 GPa were measured on films of the current polyimides. © 1999 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 37: 805–814, 1999 相似文献
11.
为了解决单季铵盐扩链剂所合成的聚氨酯对革兰氏阴性细菌不敏感的问题,文中合成了侧链带有脂肪族双季铵盐的赖氨酸作为聚氨酯的扩链剂(ED8)。用质谱、核磁共振对所合成的产物进行分析。最后,通过采用最低抑菌浓度(MIC)法对ED8进行抗菌性能测试发现,ED8对革兰氏阴性细菌的抗菌效果比单季铵盐扩链剂好8倍。 相似文献
12.
S. M. Abdul Karim Ryoji Nomura Hirotake Kajii Rahmat Hidayat Katsumi Yoshino Toshio Masuda 《Journal of polymer science. Part A, Polymer chemistry》2000,38(Z1):4717-4723
The metathesis polymerization of an anthrylacetylene bearing an alkyl ester group, 9‐(10‐hexoxycarbonyl)anthrylacetylene ( 1 ), was conducted with various transition‐metal catalysts. A completely soluble black polymer was obtained from 1 in a good yield when W‐based catalysts were employed. The polymerization at a high monomer concentration (1 M) and a high temperature (80 °C) led to the formation of poly( 1 ) with a weight‐average molecular weight of 297 × 103 in an 80% yield. The use of cocatalysts unexpectedly decreased both the yield and molecular weight of poly( 1 ). Rh‐catalyzed and Mo‐catalyzed polymerizations, however, resulted in poor yields of the polymer. The ultraviolet–visible spectrum of poly( 1 ) showed a significantly redshifted absorption (λmax = 571) with a cutoff at 780 nm, which verified the very high order of conjugation of the main chain. Poly( 1 ) exhibited the largest third‐order nonlinear optical susceptibility [χ(3) (−ω; ω, 0, 0) = − 1.9 × 10−10 esu] among the polymers from the monosubstituted polyacetylenes synthesized so far. The electrical conductivity of poly( 1 ) in an I2‐doped state was 8.77 × 10−4 at 293 K. © 2000 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 38: 4717–4723, 2000 相似文献
13.
Protoporphyrin IX dimethyl ester (PME), a dimethyl esterification of protoporphyrin IX (PpIX), exhibits higher intracellular uptake into NPC/CNE2 cells, a poorly differentiated human nasopharyngeal carcinoma, than does PpIX. Phototoxicity studies reveal PME to be a more potent photosensitizer than is PpIX, at the early and late incubation time points. Correlating phototoxicity with subcellular localization indicates that PME is a more potent photosensitizer when its primary target of photodamage is mitochondria. Also, additional targeting of lysosome enhances phototoxicity. 相似文献
14.
Azobenzenes have attracted great interest in recent years because of their ability to change conformation upon irradiation. This property has been featured in several applications not only in organic chemistry but also in biology. Even though monoazobenzenes have been extensively studied and documented in the literature, only a few methods are available for the synthesis of oligo-ortho-azobenzenes. Also, their photochemical properties have not been reported so far. This study shows an efficient strategy for the preparation of oligo-ortho-azobenzenes and the investigation of their photochemical properties. It is demonstrated that the absorption spectra are highly influenced by the substituents. Interestingly, none of the ortho-bis-, tris-, or tetra-azobenzenes showed any E → Z isomerization. Only the ortho-nitrogen-substituted monoazobenzenes' photochromic behavior upon UV irradiation was observed. 相似文献
15.
M. F. Budyka N. V. Biktimirova T. N. Gavrishova V. I. Kozlovskii 《Russian Chemical Bulletin》2008,57(7):1428-1434
Photochemical activity of azidohemicyanine (1-methyl-4-(4-azidostyryl)quinolinium iodide) was predicted by quantum chemical
calculations and confirmed experimentally. The azidohemicyanine, which was synthesized, is characterized by a long-wavelength
absorption band (LWAB) in the spectral region 350–500 nm with a maximum at 417 nm; it decomposes with a quantum yield of 0.84±0.17
upon irradiation within the LWAB, the quantum yield being independent of the presence of oxygen. The reaction products identified
by ESI mass spectrometry include the corresponding primary amine as well as azo, hydrazo, nitroso, and nitro compounds, some
of them are unidentified. The azidohemicyanine possesses the longest-wavelength visible light sensitivity among aromatic azides
known so far.
Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 7, pp. 1402–1408, July, 2008. 相似文献
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Symmetrical-A4-porphyrins bearing four fluorene donor moieties TOFP (5,10,15,20-tetra(4-(2 methyloxyfluorenyl)phenyl)porphyrin) as well as eight fluorene arms OOFP (5,10,15,20-octa(3,5-(2-methyloxyfluorenyl)phenyl)porphyrin) were synthesized and characterized. Preliminary photophysical properties are reported. In comparison to the reference tetraphenylporphyrin TPP, the luminescence properties are slightly improved. The fluorescence quantum yields of tetrafluorenylporphyrin TOFP (1) and octafluorenylporphyrin OOFP (2) are 0.10 and 0.13, respectively. 相似文献
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19.
Takashi Iizawa Tomoko Sueyoshi Chikara Hijikata Tadatomi Nishikubo 《Journal of polymer science. Part A, Polymer chemistry》1994,32(16):3091-3098
Polymers having pendant norbornadiene (NBD) moieties and rigid main chain were prepared from the reaction of partially brominated poly(2,6-dimethyl-p-phenylene oxide) with a potassium carboxylate derivative of the corresponding NBD using a phase transfer catalyst in chlorobenzene. The photochemical valence isomerization of pendant NBD to quadricyclane (QC) moieties proceeded smoothly in the film state as well as polymer solution upon the irradiation by sunlight, xenon lamp, or high-pressure mercury lamp. The rate of isomerization was affected by the structure of main chain in the polymer and the substituent groups of NBD derivatives. The catalytic reversion of the resulting QC moiety to the original NBD proceeded smoothly in the solution with (5,10,15,20-tetraphenyl-21H,23H-por-phine)cobalt(II) as the catalyst at room temperature; however, the reaction of NBD polymer containing poly(2,6-dimethyl-p-phenylene oxide) (PPO) showed lower reactivity than that of the corresponding low molecular weight QC compound. When the cycle between the photochemical valence isomerization of NBD moiety to quadricyclane (QC) moiety and thermal reversion of QC moiety to NBD moiety at 160°C was repeated, the NBD polymer synthesized from PPO degraded gradually, whereas NBD polymer prepared from poly(4-chloromethylstyrene) decomposed easily. Therefore, the rigid PPO structure showed high resistance for the degradation of NBD moiety. © 1994 John Wiley & Sons, Inc. 相似文献