Kinetic aspects of the synthesis of (2-methacryloxy)ethyloxy functionalized poly(l-lactide)
macromonomers using aluminum mono- and trialkoxides carrying this functionality are presented. The
results show the living character of the ring-opening polymerization independently of the reaction
temperature, but there are some deviations of the classical first order with respect to the monomer
concentration, particularly at 60 °C and for low monomer/aluminum catalyst ratios. The comparative
study of aluminum trialkoxides with respect to the corresponding monoalkoxides makes clear that the
polymerization initiated by trialkoxides is at least five times faster than that initiated by the monoalkoxide.
This behavior is explained by taking into consideration semiempirical calculations based on the PM-protocol, which gives an idea of the reactivity of mono- and trialkoxides with good agreement between
theoretical and experimental results.
Poly(hydroxy ether of Bisphenol-A), so-called Phenoxy resin (structure-based IUPAC name: poly[oxy(2-hydroxytrimethylene)oxy-1,4-pbenyleneisopropylidene-1,4-phenylene]), is shown to be miscible with poly(4-vinylpyridine) (P4VPy, poly[l-(4-pyridyl)ethylene]) and poly(2-vinylpyridine) (P2VPy, poly[ 1 -(2-pyridyl)ethylene]) over the entire composition range. Miscibility of the blends is evidenced by their glass transition temperatures being intermediate between the pure polymers for the blends of P4VPy and Phenoxy but being higher than the average for the case of the PZVPy/Phenoxy blends. Hydrogen bonding between the components was detected tnrough infrared spectroscopy, which was also used in the study of mixtures of low-molecular-weight analogues, in order to calculate the free energies of mixing according to the association model of Painter and Coleman. 0 1993, Huthig & Wepf Verlag, Basel CCC 0025-1 16X/93/$05.00
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