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91.
Protonation constant of an unsymmetrical Schiff base, salicylidene(N-benzoyl)glycyl hydrazone (SalBzGH), and formation constants
of its complexes have been determined potentiometrically at different temperatures in aqueous dioxane medium. Complexes of
SalBzGH with VO(IV), Mn(II), Co(II), Ni(II), Cu(II), Zn(II), Cd(II) and Hg(II) have been prepared. Elemental analyses, pH-metric,
molar conductance, magnetic susceptibility, electronic, IR, ESR, XRD (powder) and NMR studies have been carried out to study
the coordination behaviour of SalBzGH toward these metal ions. pH-metric and 1H NMR studies show the presence of two dissociable
protons in the ligand. IR and NMR spectra suggest the tridentate nature of the ligand, coordinating as a uninegative species
in the Mn(II) complex and as a dinegative species in all the other complexes. Presence of two different conformers of the
ligand at room temperature and stabilization of a single conformer upon complex formation have been established from1H NMR spectra of the metal-free ligand, Zn(II) and Hg(II) complexes recorded at 296 K. Electronic and ESR spectra indicate
highly distorted tetragonal geometry for VO(IV) and Cu(II) complexes. XRD powder patterns of the Zn(II) complexes are indexed
for an orthorhombic crystal system. 相似文献
92.
93.
Bryan B. Sauer Richard Beckerbauer Lixiao Wang 《Journal of Polymer Science.Polymer Physics》1993,31(12):1861-1872
The high sensitivity of the thermally stimulated current, thermal sampling (TS) method is emphasized in a study of the breadth of the glass transition in several liquid-crystalline polymers (LCPs). Differential scanning calorimetry (DSC) was performed on all samples to further quantify the glass transition regions. For “random” copolyester LCPs with widely varying degrees of crystallinity, including highly amorphous samples, very broad glass tran-sition regions were observed. One semicrystalline alternating copolyester and a series of semicrystalline azomethine LCPs were studied as examples of structurally regular polymers. These exhibited relatively sharp glass transitions more comparable to ordinary isotropic amorphous or semicrystalline polymers. The broad glass transitions in the random copolyesters are attributed to structural heterogeneity of the chains. In one example of a moderate-crystallinity random copolyester LCP (Vectra), glass transitions ranging up to ca. 150°C in breadth were determined by the thermal sampling (TS) method and DSC. In other lower crystallinity copolyester LCPs, the main glass transition temperature as determined by DSC was comparable to that determined by TSC although cooperative relaxations of a minor fraction of the overall relaxing species were detected well below the main Tg, by the TS method and not by DSC. Rapid quenches from the isotropic melt to an isotropic glass were possible with one LCP. The anisotropic and isotropic glassy states for this LCP were found to have the same breadth of the glass transition as was determined by the TS method, although TSC and DSC show that Tg is shifted downward by ca. 15°C in the anisotropic glass as compared to the isotropic glass. © 1993 John Wiley & Sons, Inc. 相似文献
94.
An efficient technique for drag reduction uses dilute solutions of a few p.p.m. of polymers. A possible reduction in drag of up to 80% is achieved. Several experimental observations have been made which tend to indicate that the polymers modify the turbulence structures within the buffer layer. Flow visualisations have shown that the changes consist of a weakening of the strength of the streamwise vortices. Existing literature reveals no attempts of numerical simulation of this phenomenon. In this paper an approach is pursued by using a constitutive equation which relates the elongation viscosity to the local properties of the flow. According to this model this viscosity is large in zones where the amount of strain rate is greater than the amount of vorticity, and is zero when the vorticity exceeds the strain rate. Simulations have been performed in a “minimal channel” to give good resolution with a limited number of grid points. The accuracy of the method is tested by comparison with the results of other techniques. For simulations with polymers, quantitative comparisons cannot be made, but the results reproduce the qualitative outputs of the experiments. The mean streamwise velocity is modified in the buffer layer; the peak of the streamwise turbulent intensity, in wall units, increases and its maximum moves far from the wall; and the vertical turbulent intensity is largely reduced in the wall region. An interesting outcome from both the simulation and the experiments is that the strength of the longitudinal vortices is reduced when the polymers are present. 相似文献
95.
Sk. Asrof Ali Yunusa Umar B. F. Abu‐Sharkh Hasan A. Al‐Muallem 《Journal of polymer science. Part A, Polymer chemistry》2006,44(19):5480-5494
The cycloterpolymerizations of single‐, twin‐, and triple‐tailed hydrophobes with hydrophilic monomer N,N‐diallyl‐N‐carboethoxymethylammonium chloride and sulfur dioxide afforded a series of cationic polyelectrolytes (CPEs) in excellent yields. These CPEs, upon the acidic hydrolysis of the pendent ester groups, gave the corresponding pH‐responsive cationic acid salts, which, upon a treatment with sodium hydroxide, were converted to polybetaines (PBs), anionic polyelectrolytes (APEs), and PB/APE polymers containing various proportions of zwitterionic (PB) and anionic fractions (APE) in the polymer chain. At a shear rate of 0.36 s−1 at 30 °C, salt‐free water solutions of the CPEs (2 g/dL) containing 8, 4, and 2.67 mol % of the single‐, twin‐, and triple‐tailed hydrophobes (all having 8 mol % octyloxy tails) had apparent viscosity values of 70, 2800, and 396,000 cps, respectively. The PB/APE polymer with a ratio of 33:67 for the zwitterionic and anionic fractions in the polymer chain gave the highest viscosity value. The superior viscosity behavior of the polymers containing the triple‐tailed hydrophobe was attributed to the blocky nature of the comonomer. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 5480–5494, 2006 相似文献
96.
Hans R. Kricheldorf Nino Lomadze Detlev Fritsch Gert Schwarz 《Journal of polymer science. Part A, Polymer chemistry》2006,44(18):5344-5352
5,5′,6,6′‐Tetrahydroxy‐3,3,3′,3′‐tetramethylspirobisindane was polycondensed with 1,4‐dicyanotetrafluorobenzene in four different solvents at 70 °C. In dimethylformamide, N‐methylpyrrolidone, and sulfolane exclusively, cyclic polymers were detectable by matrix‐assisted laser desorption/ionization time‐of‐flight (MALDI‐TOF) mass spectrometry up to masses around 13,000 Da. In dimethyl sulfoxide, linear byproducts were also found. Higher temperatures caused degradation reactions catalyzed by potassium carbonate. Polycondensations performed with the addition of 4‐tert‐butyl catechol or 2,2′‐dihydroxy binaphthyl yielded linear telechelic oligomers. Equimolar mixtures of linear and cyclic ladder polymers were examined by MALDI‐TOF mass spectra to determine how the end groups and the cyclic structure influenced the signal‐to‐noise ratio. The results suggested a preferential detection of the linear chains. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 5344–5352, 2006 相似文献
97.
Allison K. O'Brien Neil B. Cramer Christopher N. Bowman 《Journal of polymer science. Part A, Polymer chemistry》2006,44(6):2007-2014
The overall effects of oxygen on thiol–acrylate photopolymerizations were characterized. Specially, the choice of thiol monomer chemistry, functionality, and concentration on the extent of oxygen inhibition were considered. As thiol concentration was increased, the degree of oxygen inhibition was greatly reduced because of chain transfer from the peroxy radical to the thiol. When comparing the copolymerization of 1,6‐hexanediol diacrylate with the alkane‐based thiol (1,6‐hexane dithiol) to the copolymerization with the propionate thiol (glycol dimercaptopropionate), it was found that the propionate system was much more reactive and polymerized to a greater extent in the presence of oxygen. In addition, the functionality was considered where the glycol dimercaptopropionate was compared to a tetrafunctional propionate of similar chemistry (pentaerythritol tetrakis(mercaptopropionate)). Given the same thiol concentration, the higher functionality thiol imparted a faster polymerization rate, due to the increased polymer system viscosity, which limited oxygen diffusion and decreased the extent of overall oxygen inhibition. Thus, preliminary insight is provided into how thiol monomer choice affects the extent of oxygen inhibition in thiol–acrylate photopolymerization. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 2007–2014, 2006 相似文献
98.
C. Peinado P. Bosch V. Martín T. Corrales 《Journal of polymer science. Part A, Polymer chemistry》2006,44(18):5291-5303
The photopolymerization of bicontinuous microemulsions was simultaneously monitored with differential scanning calorimetry and fluorescence. The kinetics and mechanism of the reaction were studied throughout the entire photopolymerization reaction. The role played by the surfactant in the kinetics and morphology was studied. The nature of the surfactant changed the autoacceleration process and final conversion. The behavior was explained as a result of the differences in the interfacial properties. Anionic cetyltrimethylammonium bromide (CTAB) gave rise to a more flexible interfacial film than anionic sodium dodecyl sulfate (SDS), resulting in competition between the intramolecular and intermolecular reactions in the former systems. As cyclization did not contribute to the increase in the degree of crosslinking, SDS photopolymerization gave solids with a more rigid microstructure. Fluorescence methodology was applied to monitor bicontinuous microemulsion polymerization and to reveal the microstructure and morphology development during photopolymerization. The microemulsion composition was designed to prepare nanoporous, crosslinked materials. Even though the nanostructure of the precursor microemulsions was not retained because of phase separation during polymerization, mesoporous solids were obtained. Their morphologies depended on the nature of the surfactant, and membranes with open cells were successfully prepared with CTAB, whereas more complex morphologies resulted with SDS. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 5291–5303, 2006 相似文献
99.
Phenylene vinylene‐based electroluminescent polymers with electron transport block in the main chain
Honghao Sun Chongyu Mei Quanguo Zhou Ze Liu Dongge Ma Lixiang Wang Xiabin Jing Fosong Wang 《Journal of polymer science. Part A, Polymer chemistry》2006,44(11):3469-3478
We report a new route for the design of soluble phenylene vinylene (PV) based electroluminescent polymers bearing electron‐deficient oxadizole (OXD) and triazole (TZ) moieties in the main chains with the aryloxy linkage. Both series of the PV‐based polymers were prepared by Wittig reaction. By properly adjusting the OXD and/or TZ content through copolymerization, we can achieve an enhanced balance of hole‐ and electron injections, such that the device efficiency is significantly improved. Light‐emitting diodes fabricated from P1, P2, P3, P4, P5, P6, and P7 with the configuration of Indium–Tin Oxide (ITO)/Poly (styrene sulfonic acid) doped poly (ethylenedioxythiophene) (PEDOT)/polymer/Ca/Al, emit bright green light with the maximum peak around 500 nm. For the device using the optimal polymer (P4) as emitting layer, a maximum brightness of 1300 cd/m2 at 20 V and a maximum luminance efficiency of 0.325 cd/A can be obtained. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 3469–3478, 2006 相似文献
100.
Sridevi Kaiti Eric Fossum 《Journal of polymer science. Part A, Polymer chemistry》2006,44(6):2099-2106
A thorough study of the polymerization behavior of 4‐fluoro‐4′‐hydroxytriphenyl‐phosphine oxide, 2 , under nucleophilic aromatic substitution reactions has been carried out. The synthesis of 2 was achieved in excellent yields by the reaction of bis(4‐fluorophenyl)phenylphosphine oxide, 1 , with one equivalent of potassium hydroxide in DMSO/water. The structure and purity of 2 were confirmed via 1H, 13C, and 31P NMR spectroscopy along with elemental analysis. Polymerization reactions of 2 in NMP or DMSO at 180 °C provided the corresponding linear poly(arylene ether phosphine oxide)s, PAEPOs, with number average molecular weights, Mn, ranging from 11,700 to 36,500 Da. All of the polymer samples were completely soluble in chloroform, tetrahydrofuran, DMSO, NMP, and DMAc. The polymerization reactions were accompanied by a competing intramolecular process that resulted in the formation of cyclic oligomeric species that were removed via a final precipitation from methanol. Analysis using 31P NMR spectroscopy and size exclusion chromatography (SEC) confirmed that the majority of the lower molecular weight cyclic species were removed via this process. The polymer samples formed tough films when chloroform solutions were slowly evaporated on a glass slide. The PAEPO samples prepared in this study exhibited excellent thermal stability with Td (5%) values between 503 and 542 in air while the glass transition temperatures ranged from 223 to 237 °C. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 2099–2106, 2006 相似文献