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81.
Brad M. Rosen Virgil Percec 《Journal of polymer science. Part A, Polymer chemistry》2007,45(21):4950-4964
Atom transfer radical polymerization (ATRP) and single electron‐transfer living radical polymerization (SET‐LRP) both utilize copper complexes of various oxidation states with N‐ligands to perform their respective activation and deactivation steps. Herein, we utilize DFT (B3YLP) methods to determine the preferred ligand‐binding geometries for Cu/N‐ligand complexes related to ATRP and SET‐LRP. We find that those ligands capable of achieving tetrahedral complexes with CuI and trigonal bipyramidal with axial halide complexes with [CuIIX]+ have higher energies of stabilization. We were able to correlate calculated preferential stabilization of [CuIIX]+ with those ligands that perform best in SET‐LRP. A crude calculation of energy of disproportionation revealed that the same preferential binding of [CuIIX]+ results in increased propensity for disproportionation. Finally, by examining the relative energies of the basic steps of ATRP and SET‐LRP, we were able to rationalize the transition from the ATRP mechanism to the SET‐LRP mechanism as we transition from typical nonpolar ATRP solvents to polar SET‐LRP solvents. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 4950–4964, 2007 相似文献
82.
Novel oscillatory flow results of phenoxy/organoclay nanocomposites are analysed considering the blocking effect of nanostructure on polymer chain mobility. The modification provoked by this hindering effect on loss tangent spectrum is investigated. The study of three different systems, involving a pristine montmorillonite and two montmorillonites modified with one alkyl tail and two alkyl tails, respectively, leads to conclude that polymer-alkyl repulsive interactions play the most important role in the chain mobility obstruction process. Our results suggest that polymer-alkyl interactions increase with temperature. 相似文献
83.
84.
Binyuan Liu Yang Li Boo‐Gyo Shin Do Yeung Yoon IL Kim Li Zhang Weidong Yan 《Journal of polymer science. Part A, Polymer chemistry》2007,45(15):3391-3399
Three novel functionalized polynorbornenes (PNB) with pendant dimethyl carboxylate group (carboxylates—acetate, propionate, and butyrate) are synthesized as a vinyl‐type with a palladium (II) catalyst in high yield. The effects of size of substitutents, molar ratio of monomer to catalyst, solvent polarity, reaction time, and temperature on the polymerization of exo‐norbornene dimethyl propionate were systematically investigated. The low molar ratio and temperature, as well as high polarity of solvent, and long reaction time, are favorable for the enhancement of the monomer conversion, especially, the solvent have an obvious effect on the catalyst activity. The resulting poly(cis‐norbornene‐exo‐2,3‐dimethyl carboxylates) (PNB‐dimethyl carboxylates) show good solubility in common organic solvent and high thermal stability up to 360 °C. The glass transition temperature was detected by DMA at 331, 324, and 318 °C for acetate, propionate, and butyrate, respectively. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 3391–3399, 2007 相似文献
85.
T. V. Ramakrishnan H. R. Krishnamurthy S. R. Hassan G. Venketeswara Pai 《Journal of Chemical Sciences》2003,115(5-6):767-774
Manganites of the LA1−x
Ca
x
MnO3 family show a variety of new and poorly understood electronic, magnetic and structural effects. Here we outline a new approach
recently proposed by us, where we argue that due to strong Jahn-Teller (JT) coupling with phonons the twofold degeneratee
g
states at the Mn sites dynamically reorganize themselves into localised, JT polaronsl with exponentially small inter-site hopping, and band-like, nonpolaronic statesb, leading to anew 2-band model for manganites which includes strong Coulomb and Hund’s couplings. We also discuss some results from a dynamical mean-field theory treatment
of the model which explains quantitatively a wide variety of experimental results, including insulator-metal transitions and
CMR, in terms of the influence of physical conditions on the relative energies and occupation of thel andb states. We argue that this microscopic coexistence of the two types of electronic states, and their relative occupation and
spatial correlation is the key to manganite physics.
Dedicated to Professor C N R Rao on his 70th birthday 相似文献
86.
Leszek Wachowski Antoni Grodzicki Piotr Piszczek Monika Richert Magdalena Hofman 《Reaction Kinetics and Catalysis Letters》2007,91(1):93-99
Hydrogenation of styrene has been applied as a test reaction to study the catalytic activity of TiO2 deposited by the CVD (chemical vapour deposition) method on the surface of a carbonaceous material enriched in nitrogen (CN). 相似文献
87.
Improved reaction conditions for the preparation of poly(p‐phenylene sulfide) (PPS) directly from bis(4‐bromophenyl) disulfide (BBD) have been established. Heating BBD with magnesium metal afforded only a low molecular weight polymer. PPS with a melting temperature around 280 °C was obtained from BBD in the presence of sodium carbonate or zinc metal. The best results were obtained with the addition of a catalytic amount of KI to the zinc–BBD mixture. Polymers prepared by the above methods are semicrystalline and dissolve in 1‐chloronaphthalene and have properties comparable to commercial PPS. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 900–904, 2006 相似文献
88.
Hiroshi Aoki Ken Hosoya Tomohisa Norisuye Nobuo Tanaka Daisuke Tokuda Norio Ishizuka Kazuki Nakanishi 《Journal of polymer science. Part A, Polymer chemistry》2006,44(2):949-958
An investigation was made of the gelation of dimethacrylate‐type crosslinking agents in view of an application for separation media. The study mainly centered on a crosslinking agent, glycerol dimethacrylate (GDMA), which is relatively hydrophilic because of a hydroxyl group in the middle of its structure. The gelation of GDMA was compared with that of other hydrophobic crosslinking agents such as ethylene glycol dimethacrylate and 1,6‐hexanediol dimethacrylate. The diluents used in the study were toluene, toluene with methanol, and cyclohexanol. The gelation was observed in real time with a charge coupled device camera and dynamic light scattering (DLS). Also, the separated dry gels were extensively characterized with scanning electron microscopy, BET (N2 absorption and desorption isotherm), and Fourier transform infrared. DLS analysis showed a stronger molecular interaction of GDMA gelation in toluene, whereas this interaction was much weaker in an alcoholic solvent such as toluene with methanol or cyclohexanol. This indicated that GDMA gelation might proceed through hydrogen bonding as well as a crosslinking reaction of vinyl groups. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 949–958, 2006 相似文献
89.
Gurkan Hizal Umit Tunca Sermin Aras Humeyra Mert 《Journal of polymer science. Part A, Polymer chemistry》2006,44(1):77-87
Copper‐catalyzed controlled/living radical polymerization (LRP) of styrene (St) was conducted using the silica gel‐supported CuCl2/N,N,N′,N′,N″‐pentamethyldiethylenetriamine (SG‐CuCl2/PMDETA) complex as catalyst at 110 °C in the presence of a definite amount of air. This novel approach is based on in situ generation and regeneration of Cu(I) via electron transfer reaction between phenols and Cu(II). Sodium phenoxide or p‐methoxyphenol was used as a reducing agent of Cu(II) complexes in LRP. The number–average molecular weight, Mn,GPC, increases linearly with monomer conversion and agrees well with the theoretical values up to 85% conversion The molecular weight distribution, Mw/Mn, decreases as the conversion increases and reaches values below 1.2. The catalyst was recovered in aerobic condition and reused in copper‐catalyzed LRP of St. For the second run, the number–average molecular weights increased with monomer conversion and the polydispersities decreased as the polymerization proceeded and reached to the value <1.3 at 81% conversion. The recycled catalyst retained 90% of its original activity in the subsequent polymerization. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 77–87, 2006 相似文献
90.
Vasilis P. Barberis John A. Mikroyannidis 《Journal of polymer science. Part A, Polymer chemistry》2006,44(11):3556-3566
A poly(p‐phenylenevinylene) derivative (PPV–TPA)] and a series of statistical copolyfluorenes (PF–TPA)] containing oxadiazole and triphenylamine segments along the main chain were synthesized by the Heck reaction and nickel‐mediated coupling, respectively. The PF–TPA copolyfluorenes with relatively low contents of oxadiazole and triphenylamine units were readily soluble in common organic solvents, whereas the other copolyfluorenes displayed lower solubility. PPV–TPA showed excellent solubility in solvents such as tetrahydrofuran (THF), dichloromethane, chloroform, and toluene. Thin films of the polymers absorbed light in the range of 375–396 nm and had optical band gaps of 2.76–2.98 eV. They emitted blue‐green light with a maximum at 414–522 nm. The fluorescence quantum yields in THF solutions were 0.08–0.53. The copolyfluorene PF–TPA thin films with high contents of oxadiazole and triphenylamine moieties emitted pure blue light that remained stable even after annealing at 150 °C for 4 h in air. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 3556–3566, 2006 相似文献