Degradative chain transfer in vinyl acetate polymerizations using toluene as solvent

In this work, we propose that retardation in vinyl acetate polymerization rate in the presence of toluene is due to degradative chain transfer. The transfer constant to toluene (C_trs) determined using the Mayo method is equal to 3.8 × 10^?3, which is remarkably similar to the value calculated from the rate data, assuming degradative chain transfer (2.7 × 10^?3). Simulations, including chain‐length‐dependent termination, were carried out to compare our degradative chain transfer model with experimental results. The conversion–time profiles showed excellent agreement between experiment and simulation. Good agreement was found for the M_n data as a function of conversion. The experimental and simulation data strongly support the postulate that degradative chain transfer is the dominant kinetic mechanism. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 3620–3625, 2007     

Structure of norbornene-fused 3,1-oxazine double cycloadducts

Pentacyclic isoxazolines were obtained by the cycloaddition of benzonitrile oxide to norbornene-azetidinone-fused 3,1-oxazines. The constitutions of two of the isomers obtained, and the configurations and conformations of all products, were determined by means of ¹H and ¹³C NMR spectroscopy and DNOE experiments.     

Galactic model of element formation

A cosmological model is presented that produces He, C, O, D, Li, Be, and B in their observed abundances without a Big Bang. The elements are produced during the 1.5-Gy formation period of a galaxy, with C, O, and other heavy elements produced by stars of M>12 M₃ , He by stars of 6 M_s<M<12 M_s, and D, Li, Be, and B by cosmic-ray reactions in a nearly pure H plasma halo. Thus, the model shows that the major elements used in astrophysical studies can be produced during galactic formation by exactly the same processes known to function today at much lower rates     

A Symmetric-Impulse Approximation Applied to the Faddeev Theory on the Charge Transfer Amplitude

Off-the-shell anomalous factors of the two-body Coulomb transition matrices appear in the integral form of the Faddeev second-order nuclear-electronic amplitude, for proton-hydrogen charge transfer scattering in a typical nlm → n′l′m′ transition. A symmetric-impulse approximation (SIA) is applied to eliminate these factors and an induction method is proposed to analytically calculate the remaining integrals. The nuclear-electronic amplitude is derived for the general case, and for totally symmetric collisions, in terms of generalized hypergeometric functions of two variables, F ₄, and of one variable, ₃ F ₂, respectively. The angular distribution of the second-order nuclear-electronic charge transfer amplitude shows the Thomas mechanism as a peak or a hump for symmetric and asymmetric collisions. There also exists a peak in the forward angular distribution of the second-order nuclear-electronic amplitude, which partly cancels the kinematic peak in the angular distribution of the charge transfer differential cross sections.     

Matching in a class of stationary axisymmetric perfect fluid solutions of Einstein's equations

The class of previously found stationary axisymmetric perfect fluid solutions of Einstein's equations is written inh-orthogonal coordinates,h being a space-like coordinate. Matching of a big number of solutions of the class with each other seems to be possible for a proper choice of some parameters. The exterior solutions of the class are matched explicitly with interior solutions. Also, interior solutions are matched explicitly with each other.     

Dynamic mechanical thermal analysis transitions of partially and fully substituted cellulose fatty esters

The main transitions of cellulose fatty esters with different degrees of substitution (DSs) were investigated with dynamic mechanical thermal analysis. Two distinct main relaxations were observed in partially substituted cellulose esters (PSCEs). They were attributed to the glass‐transition temperature and to the chain local motion of the aliphatic substituents. The temperatures of both transitions decreased when DS or the number of carbon atoms (n) of the acyl substituent increased. Conversely, all the transitions of fully substituted cellulose esters occurred within a narrow temperature range, and they did not vary significantly with n. This phenomenon was explained by the formation of a crystalline phase of the fatty substituents. The presence of few residual OH groups in PSCEs was responsible for a large increase in the storage bending modulus, and it eliminated the effect of n on damping. © 2002 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 41: 281–288, 2003