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101.
P. W. Moore J. G. Clouston R. P. Chaplin 《Journal of polymer science. Part A, Polymer chemistry》1983,21(8):2503-2511
The effects of pressure, irradiation dose rate, and emulsifier concentration on the rate of polymerization of styrene emulsions stabilized with a nonionic surfactant, Teric GX13, were investigated. Results differed from those previously obtained with anionic surfactants and did not follow Smith–Ewart kinetics. The controlling influence of the surfactant at the particle–water interface on the reaction was demonstrated and results could be interpreted in terms of the Medvedev equation. Using this equation, we determined a value for the activation volume for chain propagation, ΔV, as ?18.7 cm3 mol?1. This value is the same as that for pure styrene and emulsions that follow Smith–Ewart kinetics. 相似文献
102.
P. W. Moore J. G. Clouston R. P. Chaplin 《Journal of polymer science. Part A, Polymer chemistry》1981,19(7):1671-1678
The pressure dependence of the termination rate constant kt for the free radical polymerization of monomers such as styrene is a function of polymer chain length, chain stiffness, and monomer viscosity, all of which influence the rate of segmental diffusion of an active radical chain end out of the coiled polymer chain to a position in which it can react with a proximate radical. Although kt is not sensitive to changes in chain length, the large increase in molecular weight is responsible for a significant reduction in kt at high pressures. For most of the common vinyl polymers, which exhibit some degree of chain stiffness, kt is inversely proportional to a fractional power of the monomer viscosity because it depends in part on the resistance of chain segments to movement and in part on the influence of viscosity in controlling diffusion of the chain ends. The fractional exponent appears to increase with pressure and this is interpreted as evidence that the polymer chains become more flexible in a more viscous solvent. Because the fractional exponent is higher for more flexible chains, the value of the activation volume for chain termination is an indication of the degree of flexibility of the polymer chains, provided that the monomer is a good solvent for the polymer and that chain transfer is negligible. 相似文献
103.
John F. Quinn Rodney P. Chaplin Thomas P. Davis 《Journal of polymer science. Part A, Polymer chemistry》2002,40(17):2956-2966
Reversible addition–fragmentation chain transfer (RAFT) polymerization has been shown to be a facile means of synthesizing comb, star, and graft polymers of styrene. The precursors required for these reactions were synthesized readily from RAFT‐prepared poly(vinylbenzyl chloride) and poly(styrene‐co‐vinylbenzyl chloride), which gave intrinsically well‐defined star and comb precursors. Substitution of the chlorine atom in the vinylbenzyl chloride moiety with a dithiobenzoate group proceeded readily, with a minor detriment to the molecular weight distribution. The kinetics of the reaction were consistent with a living polymerization mechanism, except that for highly crowded systems, there were deviations from linearity early in the reaction due to steric hindrance and late in the reaction due to chain entanglement and autoacceleration. A crosslinked polymer‐supported RAFT agent was also prepared, and this was used in the preparation of graft polymers with pendant polystyrene chains. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 2956–2966, 2002 相似文献
104.
Chaplin AB Harrison JA Nielson AJ Shen C Waters JM 《Dalton transactions (Cambridge, England : 2003)》2004,(17):2643-2648
Reaction of one equivalent of tris(3,5-di-tert-butyl-2-hydroxy)methane with TaCl5 in CH2Cl2 along with Et3N gave a solid which on prolonged crystallisation led to a small quantity of crystalline material. An X-ray crystal structure determination showed one crystal was [TaCl3[[OC6H2(CMe3)2-2,4]3CH]]- Et2NH2+.3C6H6.1.5H2O with the anion consisting of three chloro ligands and three phenoxides of the tripodal ligand about the tantalum centre. The triphenylmethyl group proton was located and refined and was found to be enclosed in a cage making contacts of 2.09(8), 2.09(8) and 1.89(12)A with the phenoxide ligand oxygens consistent with weak C-H bond hydrogen bonding. The hydrogen atom points at the tantalum atom at a distance of 2.14(11) A from it, the TaH-C angle is 166 degrees and the C-H bond distance is 1.04(12) A. DFT calculations at the B3LYP level indicate that where a hydrogen atom is attached to the triphenylmethyl carbon on the inside of the cage, there is good agreement with the crystal structure. The C-H bond points directly at the tantalum centre and an NBO analysis indicates there is significant overlap of the triphenylmethyl C-H bond electron density in a linear sense with an "unfilled" metal d orbital. Based on the NBO analysis, the C-HTa overlap would appear to be an example of a linear agostic interaction under the definition of agostic bonding. 相似文献
105.
A convenient method for the synthesis of 2-bromo-3-aroyl-benzo[b]furans from readily accessible precursors has been developed. The 2-bromo group has been employed as a versatile synthetic handle in both palladium-mediated couplings and direct nucleophilic substitutions to give access to a wide range of 2-substituted-3-aroyl-benzo[b]furans. 相似文献
106.
Terminal Alkyne Coupling Reactions through a Ring: Mechanistic Insights and Regiochemical Switching
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Caroline M. Storey Dr. Matthew R. Gyton Dr. Rhiann E. Andrew Dr. Adrian B. Chaplin 《Angewandte Chemie (International ed. in English)》2018,57(37):12003-12006
The mechanism and selectivity of terminal alkyne coupling reactions promoted by rhodium(I) complexes of NHC‐based CNC pincer ligands have been investigated. Synthetic and kinetic experiments support E‐ and gem‐enyne formation through a common reaction sequence involving hydrometallation and rate‐determining C?C bond reductive elimination. The latter is significantly affected by the ligand topology: Employment of a macrocyclic variant enforced exclusive head‐to‐head coupling, contrasting the high selectivity for head‐to‐tail coupling observed for the corresponding acyclic pincer ligand. 相似文献
107.
D. H. Chaplin X. Huang W. D. Hutchison G. A. Stewart N. Yazidjoglou 《Hyperfine Interactions》1993,80(1-4):1263-1267
High resolution magnetic and electric hyperfine interaction distributions are determined for single crystal54MnNi with diffused impurity concentrations of 0.14 and 0.40 at%, and for a 0.1 µm layer of60CoFe co-plated onto single crystal Fe. High quality gamma detected nuclear spin echoes recorded for the60CoFe specimen demonstrate that a reduced influence of the RF skin effect far outweighs any magnetic hyperfine field interaction broadening associated with the co-plating process. 相似文献
108.
W. D. Hutchison G. A. Stewart S. J. Harker D. H. Chaplin 《Hyperfine Interactions》2004,159(1-4):121-125
57FeFe with isotopic concentrations from 15 to 95% is studied using NMR thermally detected by nuclear orientation. Lines are found to be consistently homogeneous. The contrast with previous inhomogeneous 57FeFe lines from Mössbauer detected NMR is explained by differences in radio frequency field strength. 相似文献
109.
Results of isochronal anneals following electron irradiaton of copper single crystals indicate the IB recovery is enhanced for a (100) sample compared to the IB recovery for a (110) sample and a polycrystal sample. Comparison of these results with data from aluminum single crystals indicates a tentative assignment of the IB defect in copper to damage produced in the (100) direction. 相似文献