Rapid and controlled synthesis of hydrophobic polyethers by monomer activation

A series of polyethers was prepared by monomer-activated anionic polymerization. The combination of an ammonium salt with triisobutylaluminum allowed the polymerization of epoxides containing various aliphatic side chains (1,2-butene oxide (BO), 1,2-hexene oxide (HO), and 1,2-octadecene oxide (ODO)) or a fluorinated group (3,3,3-trifluoro-1,2-epoxypropane (TFEP)). Polymers of molar masses up to 35 000 g/mol with relatively narrow molar mass distribution could be synthesized. Polymer structures were analyzed by 13C NMR, and the thermal behavior was studied by differential scanning calorimetry (DSC). The evolution of hydrophobicity was investigated according to the length and composition of the side chain. Using a long aliphatic side-chain epoxide (C16) imparted crystallinity to the resulting atactic polymer.

Study of tacticity and thermal rearrangement of low molecular weight 1,2- polybutadiene by NMR

Low molecular wieght 1,2-polybutadiene (Aldrich) tacticity was determined by 13CNMR (100.6 MHz). It was found that the olefinic methylene carbon has the highest splitting and a combination of pentad and heptad sequences was determined which is in agreement with the theoretical calculations. For the first time aliphatic methine carbon assignment of 1,2-polybutadiene was performed. Furthermore, olefinic methine carbon assignment was also performed and the results were compared with the theoretical calculations. For all carbons Bernoullian and first-order Markov-chain propagation statistics were used to fit the experimental data and a good agreement was obtained indicating an atactic polymer (Pm= 0.467). It was shown that the most probable reaction before gelation which happens by heating the polymer under vacuum at 250°C, is crosslinking accompanied with methyl group formation. The decrease in double bond intensity of the pendant group together with constant cis and trans double bond intensities were observed. During heating the syndiotactic triad sequences are consumed indicating that no cyclization has happened.