Synthesis of ethylene-styrene copolymer containing syndiotactic polystyrene sequence by trivalent titanium catalyst

We describe the synthesis of a styrene-ethylene copolymer using a trivalent titanium-based polymerization catalyst system, tris(acetylacetonate)titanium (Ti(acac) ₃), combined with triisobutylaluminum-modified methylaluminoxane. Gel-permeation chromatography measurement revealed that copolymerization using the above-mentioned catalyst system yielded a mixture of two different polymers. ¹³C nuclear magnetic resonance (NMR) analysis of the Soxhlet-extracted fractions indicated that the insoluble part contained a long ethylene-ethylene sequence and an isolated styrene unit, whereas the soluble part contained a syndiotactic styrene-styrene sequence with ethylene units adjacent to continuous styrene units. The ratio of the styrene-styrene sequence to the styrene-ethylene joint part of the Soxhlet-soluble fraction, estimated from the NMR resonances, increased with the styrene content. The melting temperature of the Soxhlet-soluble fraction also increased with the (styrene-styrene)/(styrene-ethylene) ratio of the polymers. These two results together indicate that a block-like copolymer was produced that contained long syndiotactic polystyrene portions separated by ethylene units.