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Dax Kukulj Thomas P. Davis Kevin G. Suddaby David M. Haddleton Robert G. Gilbert 《Journal of polymer science. Part A, Polymer chemistry》1997,35(5):859-878
The behavior of catalytic chain transfer in semi-batch emulsion polymerization has been studied for two monomers, viz, methyl and n-butyl methacrylate. Two different catalytic chain transfer reagents were used with different water solubilities: cobaloxime boron fluoride (COBF), which was found to partition approximately equally between organic and aqueous phases, and tetra-phenyl cobaloxime boron fluoride (COPhBF), which was found to reside predominantly in the organic phase. The difference in hydrophilicity between the two transfer agents was found to affect the polymerization mechanism. COBF exhibited superior transfer behavior in all cases, whereas the restricted mobility of the COPhBF had a deleterious effect on the efficiency of the transfer mechanism. The best results were achieved under monomer flooded conditions using COBF. MALDI-TOF mass spectrometry analysis shows catalytic chain transfer to be the dominant mechanism initiating and stopping chain growth as none of the chains appear to have initiator fragment end groups. Analysis of copolymers by MALDI-TOF mass spectrometry reveals both molecular weight and composition data. © 1997 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 35: 859–878, 1997 相似文献
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Kevin D. Belfield Feras B. Abdelrazzaq 《Journal of polymer science. Part A, Polymer chemistry》1997,35(11):2207-2219
Photoinitiated polymerization of 4-methylene-2-phenyl-1,3-dioxolane ( 1 ) was carried out using either tris (4-methylphenyl) sulfonium hexafluoroantimonate or 4-decyloxyphenyl phenyliodonium hexafluoroantimonate as initiators. 1H-NMR analyses confirmed exclusive ring-opening while DSC and SEC were used to determine the glass transition temperatures (Tgs) and molecular weights, respectively. Photoinitiated cationic copolymerizations of 1 were investigated with several acyclic and cyclic monomers. Copolymerization of 1 with vinyl ethers and a spiroorthoester resulted in copolymers whose thermal properties were dependent on comonomer ratios. Copolymers of 1 and dihydrofuran or dihydropyran afforded soluble polymers with Tgs significantly higher than the homopolymer of 1 . © 1997 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 35 : 2207–2219, 1997 相似文献
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A technique for rapid determination of the presence of polystyrene in individual micron-diameter polymer particles of mixed composition is presented. This technique is based upon observation of visible emission from conjugated regions of the polymer backbone, generated photochemically, while the particle is held in an optical trap. Particle emission characteristics are dependent upon particle size and suspending solvent. Emission spectra are provided for single component polystyrene particles and mixed polymer particles containing poly(methyl methacrylate), poly(N-vinyl pyrrolidone), and polystyrene. © 1998 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 36: 999–1004, 1998 相似文献
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Christopher B. Smith Stephen F. Lincoln Max R. Taylor Kevin P. Wainwright 《Acta Crystallographica. Section C, Structural Chemistry》2003,59(9):m358-m360
Crystallization of [Cd(S‐thpc12)](ClO4)2·H2O {S‐thpc12 is 1,4,7,10‐tetrakis[(S)‐2‐hydroxypropyl]‐1,4,7,10‐tetraazacyclododecane} in the presence of two equivalents of sodium picrate monohydrate (sodium 2,4,6‐trinitrophenolate monohydrate) diastereoselectively produces a neutral receptor complex, viz. the title compound, Λ‐[Cd(C20H44N4O4)](C6H2N3O7)2·CH3CN. In this complex, two picrate anions hydrogen bond, via their phenolate moieties, to the pendant hydroxyl groups of the receptor which, together with the four N atoms, themselves bond to CdII in an approximately cubic arrangement. One picrate anion hydrogen bonds to all four hydroxyl groups, one of which also acts as the sole hydrogen‐bond donor to the second picrate anion. 相似文献
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The present study examines the feasibility of combining the correlation‐consistent basis sets developed by Dunning and coworkers with the hybrid Hartree–Fock/density functional method B3LYP. Furthermore, extrapolation to the complete basis set (CBS) limit minimizes errors due to the presence of an incomplete basis set and can act as a rigorous test of the limitations of the B3LYP method. Equilibrium geometries, energies, and harmonic vibrational frequencies were determined for a series of well‐studied, yet computationally challenging, small inorganics and their respective ions. The results were then extrapolated to the CBS limit, where applicable, and compared to experiment. It was found that a union between the hybrid Hartree–Fock/density functional B3LYP method and Dunning's augmented correlation‐consistent basis sets gave results that were comparable to molecular orbital methods that explicitly account for electron correlation. Furthermore, the minimum basis set necessary to attain reasonable results for the systems studied was aug‐cc‐pVTZ. Upgrading to the aug‐cc‐pVQZ level and subsequent extrapolation to the CBS limit further improved the overall agreement with the experiment. ©1999 John Wiley & Sons, Inc. J Comput Chem 20: 207–216, 1999 相似文献