Photophysics of carbazole-containing systems. 1. Dilute solution behavior of poly(N-vinyl carbazole) and N-vinyl carbazole/methyl acrylate copolymers

Steady-state and time-resolved fluorescence techniques have been used to study the photophysical behaviors of poly(N-vinyl carbazole), PNVCz and a series of N-vinyl carbazole-methyl acrylate (NVCz-co-MA) copolymers in dilute solution as a function of both NVCz composition and temperature. A kinetic scheme, intended to describe intramolecular excimer formation across the entire NVCz composition range, is proposed. In low aromatic content copolymers, two monomer species (unquenched and quenched monomer) and two excimer species (the sandwich-like excimer and a higher energy excimer) exist. The contribution from monomer emission to the overall fluorescence decreases with increasing NVCz content through increased excimer formation: this is likely to be consequent upon (1) an increase in the number of excimer forming sites, and (2) increasing efficiency of energy transfer from the excited monomers to the excimer forming sites. In the homopolymer, PNVCz, the only emission that can be observed on a nanosecond timescale is excimeric. This fluorescence appears to originate from three excimer species (the sandwich-like excimer, and two higher energy forms). For the homopolymer, the current observations are consistent with the model proposed by Vandendriessche and De Schryver [Polym. Photochem. 7 , 153 (1986)]. © 1997 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 35 : 963–978, 1997     

Intersequence cyclization in copolymers of N-vinyl carbamates

Monomer reactivity ratios determined for the copolymerization of tert-butyl N-vinylcarbamate (r_A = 0.55 ± 0.05) with phenyl N-vinylcarbamate (r_B = 2.08 ± 0.15) indicate that the monomer units are distributed randomly along the polymer chains. The following sequence of reactions was used to cause intersequence cyclization between tert-butyl N-vinylcarbamate and phenyl N-vinylcarbamate units in the copolymers. The extent of cyclization obtained was in accord with that expected for random copolymers.      

Photopolarization and depolarization characteristics of poly(N-vinyl carbazole)

The photoelectret properties of poly(N-vinyl carbazole) sandwiched between a conducting glass electrode and an aluminum electrode have been studied. Photoelectret polarization was carried out by simultaneous application of an electric field and ultraviolet illumination. The polarization exhibits a linear dependence on the polarizing voltage, polarization time, and illumination intensity, with saturation effects for large values of these parameters. The depolarization current decay is quite fast, which indicates the absence of deep-trap levels. The ratio of photoelectret charge to the dark polarization charge is found to be 100, which determines the image contrast if the polymer film is used in persistent internal polarization (PIP) electrophotography.     

The copolymerisation of 2,4-dicyanobut-1-ene with N-vinyl carbazole

The copolymerisation of the monomers 2,4-dicyanobut-1-ene and N-vinyl carbazole has been studied. The presence of a charge transfer complex from these two monomers with a 1:1 stoichiometry has been established, and a value of 0.22 dm³ mol⁻¹ at 298 K for the equilibrium constant for complex formation has been obtained from NMR measurements. The copolymer composition data have been analyzed allowing for the participation of the complex in the propagation reactions; the results have been compared with the predictions of two simpler terminal models and with the penultimate model.     

Spectroscopic evidences for grafting of N-vinyl carbazole on cellulose-acetate film

N-vinyl carbazole (VCZ) was grafted on cellulose acetate film using simultaneous cobalt-60-γ ray irradiation grafting technique. Absorption, excitation, and emission spectral studies on the grafted film were carried out to ascertain the grafting of VCZ on the polymer matrix. Laser-flash photolysis studies with the solution of grafted film indicate the opening of the double bond of VCZ, which leads to the grafting. On the basis of the observed results, the mechanism of grafting in the system was proposed. © 1994 John Wiley & Sons, Inc.     

Optical sensitization of charge carrier transport in poly(N-vinyl carbazole)

Abstract— The photoconductivity of thin films of poly(N-vinyl carbazole), and poly(N-vinyl carbazole) sensitized with a thin layer of amorphous selenium, has been measured using a ‘xerographic’ condenser discharge technique and a conventional time of flight light pulse photo-response technique. Direct camer generation and hole mobility in the polymer was found to be strongly field dependent. There appears to be no evidence for deep trapping. Hole transport through the polymer was able to be sensitized by light absorbed in the selenium. The results indicate that the photosensitization mechanism can be thought of in terms of hole generation and transport in selenium, field-modulated injection across the selenium polymer interface and transport through the polymer.     

Radiation-induced graft copolymerization of N-vinyl carbazole and methyl methacrylate onto cellulose acetate film

N-Vinyl carbazole methyl methacrylate, and the binary mixtures of these monomers were grafted onto cellulose acetate films by taking recourse to Co-60 simultaneous irradiation grafting technique. The effect of various parameters (e.g., solvents, radiation dose, compositions of the monomers, and concentration of the monomers) on the extent of grafting in unitary and binary systems were studied. The optimum conditions for grafting were evaluated. The sensitizing effect of one monomer in the presence of other in the binary system was identified. The relative molecular reactivity and reactivity ratios were computed and these were used in explaining sensitization and the effect of monomer compositions on the extent of grafting in the binary system.     

Structure and hydrolytic activity of N-vinyl derivatives of phenothiazine,carbazole and acridone

Conclusions An interrelationship of reactivity, and the geometric and electronic structure of N-vinyl derivatives of phenothiazine, carbazole, and acridone was established on the basis of a kinetic study and¹H and¹³C NMR spectral measurements.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 2, pp. 444–447, February, 1987.     

聚N-乙烯基己内酰胺及其共聚物的合成与应用

综述了聚N-乙烯基己内酰胺(PNVCL)及其共聚物的合成与用途研究现状,评述了不同聚合方法。指出了聚N-乙烯基己内酰胺系列聚合物在各个领域的应用前景及开发策略。     

C60接枝聚(N-乙烯基咔唑)的合成、表征及光电导性能

自从Ｃ６０被发现和被制备出来以后,其特殊的结构和独特的物理和化学性质受到各研究领域学者的广泛青睐．聚（Ｎ－乙烯基咔唑）（ＰＶＫ）体系经 Ｃ６０掺杂后光电导性能有很大幅度提高．但掺杂体系不稳定,因而限制了对该类材料的应用．为了克服这种缺点,我们尝试用各种简单的方法把Ｃ６０化学键合到高分子链中,制备具有光电导性能的Ｃ６０高分子衍生物． 最近,唐本忠［１］和 Ｐａｔｉｌ［２］等分别用常规的自由基聚合方法,将Ｃ６０接枝到聚合物分子主链上,我们已研究了不含导电高分子的Ｃ６０共聚物的光电导性能［３］,本文采用…     

Synthesis and properties of a star-shaped organic material with triphenylamine and N-vinyl carbazole units

A starburst triphenylamine cored N-vinyl carbazole (V-Cz) branched compound was designed and synthesized via optimized Heck reaction in a yield of 40-60%.Moderate yield came from decomposition of V-Cz and self-coupling of triiodo-triphenylamine. TCz-TPA adopts a highly twisted propeller conformation by molecular mechanical optimization.It is readily soluble for its highly twisted conformation.Transparent and pinhole free films could be easily fabricated by spin-coating for its starburst structure.It emits blue-greenish light in CH_2Cl_2 peaked at 460 nm with a narrow full-width at half-maximum (FWHM) of 65 nm.As compared, the absorption peaks of the spin-coated film blue shifted and emission peak red shifted to 510 nm with a FWHM of 96 nm.     

Ring opening process of some spirochromenes by photoproduced HCl in poly(N-vinyl carbazole)

The coloration reaction of some spirochromenes (SP) has been investigated in the case of a free radical photosensitive system composed of a poly(N-vinylcarbazole) matrix (PVCz) in dichloromethane containing carbon tetrachloride as an activator at average ratios of 5:1:0.1 for PVCz, CCl₄ and SP, respectively. In this system, photoproduced HCl leads to the formation of the colored forms of SP. Acidification and irradiation of the variety of spirochromene solutions in the presence and absence of PVCz were also investigated and compared with the effect of photoproduced HCl on the reversibility of the ring opening process. The opened forms of the compounds were characterized by UV–visible spectra, pH and conductivity measurements. The effect of solvent and the substituent of SP were investigated. Decoloration reactions of the opened forms of SP at 50°C were followed using UV–visible spectroscopy, pH and conductivity measurements. © 1997 John Wiley & Sons, Ltd.     

Cationic polymerization of N-vinyl carbazole by trityl salts—I.: Reactivity of propagating species

The cationic polymerization of N-vinyl carbazole, initiated by Ph₃C⁺ AsF₆^? and Ph₃C⁺ PF₆^? in methylene dichloride at 20 and 0°, has been studied in some detail. Reactions were very fast and rates of monomer consumption were measured using an adiabatic calorimetric technique. Initiation was relatively “slow” but complete, and termination was deduced to be insignificant during kinetic lifetimes. Values for k_p were found to vary with the initial initiator concentration; this dependence is discussed in terms of current theories regarding equilibria between ion pairs and free ions in non-aqueous solvents. k_p⁺ values estimated from two methods of extrapolation are 9.5 · 10⁵ M^?1 sec^?1 at 20° and 4.8 · 10⁵ M^?1 sec^?1 at 0°. Finally, it has been found that ion pairs are much less reactive than free ions in this system.     

Solution properties of poly(N-vinyl carbazole)—III: Excluded volume theories and theta temperature

Thermodynamic properties of dilute solutions of poly-N-vinylcarbazole have been studied by viscometry in chlorobenzene and nitrobenzene at several temperatures. The validities of some excluded volume theories have been tested and the unperturbed dimensions have been calculated; for two of these theories in particular, no dependence of unperturbed dimensions on temperature and solvent has been found. The viscometric equations have also been determined. The theta temperatures for PNVC in chlorobenzene and nitrobenzene are ? 36.5 and ? 20.4°C respectively.     

Magnetic field effect on an exciplex between N-vinyl carbazole grafted on cellulose acetate film and 1,4-dicyanobenzene

The present work emphasises the investigation of photoinduced electron transfer reaction between an electron-donor fluorophore, N-vinyl carbazole (VCZ), grafted on a polymeric cellulose acetate film and an electron-acceptor, 1,4-dicyanobenzene, in the presence of an external magnetic field that serves as a powerful tool to identify the spin states where the initial electron transfer occurs and to modulate the course of the reaction as desire. Here initial electron transfer occurs in the singlet spin state, and the formation of exciplex increases in the presence of magnetic field. The maximum field effect is obtained in the solvent with medium dielectric constant (ε_max) around 8.0. The ε_max value indicates that the extent of charge transfer in this exciplex is less compared to other similar systems studied so far, owing to the characteristic binding of VCZ to the polymeric backbone through oxygen atom. © 1999 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 37: 3910–3915, 1999     

Cationic polymerization of N-vinyl carbazole by trityl salts—II.: New considerations about the mechanism

The mechanism of initiation in the polymerization of N-vinyl carbazole by trityl salts in methylene dichloride has been investigated by spectroscopic studies of final reaction mixtures and molecular weight analysis. The proposed reaction mechanism involves regeneration of the Ph₃C⁺ cation and propagation through a dication as active species.     

Synthesis and optical properties of white phosphorescent carbazole - iridium copolymers

A series of novel carbazole-iridium copolymers have been designed and synthesized by the combination of blue-emitting acrylate carbazole M1 with hole transporting property and yellow-emitting cyclometalated iridium complex M2 containing 2-phenylpyridine as main ligand and acrylic acid as auxiliary ligand. The results showed that the blue carbazole host resulted in an efficient energy transfer to the yellow iridium complex guest, and when the feed molar ratio of M1 to M2 was 99:1, the emission spectrum of the copolymer presented a broad peak emission which can cover the whole visible range from 400 to 700 nm to obtain a nearly white copolymer material with the CIE coordinates of (0.30, 0.31), as a consequence of polymerized units luminescence, host-guest energy transfer and conjugation degree. Nevertheless, the host-guest energy transfer resulted in green emission about 524 nm of copolymer as the proportion of iridium complex monomer increased. The fluorescence quantum yields of the copolymers were significantly improved compared to the iridium complex monomer.     

Synthesis of N,N-dimethylaminoethyl methacrylate copolymers with N-vinyl caprolactam and their complexing and flocculating behavior

Thermosensitive copolymers of N-vinyl carprolactam with N,N-dimethylaminoethyl methacrylate have been synthesized via free-radical polymerization, and reactivity ratios in dioxane have been estimated as 2.44 and 0.07, respectively. It has been shown that temperatures of phase separation for 1% aqueous solutions of homopolymers are close and remain virtually unchanged with the copolymer composition. The efficiency of flocculating behavior of copolymers with respect to a polystyrene latex has been estimated from the initial rate of flocculation as a function of the polyelectrolyte concentration in an acidic medium.     

Copolymerization of N-vinylcaprolactam with N-vinyl(benz)imidazoles and the properties of aqueous solutions of the copolymers

The free-radical solution copolymerization of N-vinylcaprolactam with 1-vinylimidazole, 1-vinyl-2-methylimidazole, 1-vinyl-2-methyl-3-propylimidazolium iodide, or 1-vinyl-2-methylbenzimidazole was investigated and the monomer reactivity ratios in the copolymerization were calculated. It was shown that 1-vinylimidazole exhibits a relatively higher activity in the copolymerization as compared to the monomers that bear substituents on the ring. It was established that, except for the copolymers of 1-vinyl-2-methylbenzimidazole, water-soluble products could be obtained. Aqueous solutions of N-vinylcaprolactam copolymers with N-vinyl(methyl)imidazoles were found to have a higher phase separation temperature relative to poly(N-vinylcaprolactam) solutions. The thermal stability of the aqueous solutions increases with a rise in the amount of hydrophilic 1-vinyl-and 1-vinyl-2-methylimidazole units in macromolecular chains and in the presence of NaCNS or KBr. The effect of salts on the thermal stability of aqueous copolymer solutions has the same character as in the case of the N-vinylcaprolactam homopolymer.