Cyclopentadienyl ligand melting points

Modification of the cyclopentadienyl ligands has led to a very rich chemistry and today a great variety of microstructures and combination thereof can be synthesised as desired including isotactic polymer with melting points above 160 °C, syndiotactic polypropene [16], block polymers, hemi-isotactic polymers etc. 

Each set of experiments was carried out under the same reaction condition except using different comonomers, i.e. p-methylstyrene, o-methylstyrene, m-methylstyrene and styrene, respectively. The compositions of copolymers were determined by H NMR spectra, and the thermal properties (melting point and crystallinity) were obtained by DSC measurements. Overall, all comonomers show no retardation to the catalyst activity. In fact, the significantly higher catalyst activities were observed in all copolymerization reactions (runs 2-5), comparing with that of ethylene homopolymerization (run 1). Within each set (runs 2-5 and 6-9) of comparative experiments, p-methylstyrene consistently shows better incorporation than the rest of comonomers, i.e. o-methylstyrene, m-methylstyrene and styrene. Both catalysts with constrained mono- and di-cyclopentadienyl ligands are very effective to incorporate p-methylstyrene into polyethylene backbone. In runs 2 and 6, more than 80 % of p-methylstyrene were converted to copolymer within one hour under constant (- 45 psi) ethylene pressure. On the other hand, only less than half of styrenes (runs 5 and 9) were incorporated into ethylene copolymers under the same reaction conditions. The significantly... 

Table VI provides a comparison of the catalytic activities of various zir-conocenes and one hafnocene measured under the same conditions, along with the product molecular weight, isotacticity, and melting point. The bisin-denyl compounds show high activity, but the activities of the hafnocene and the mixed (indenyl)cyclopentadienyl compounds are significantly lower. The ligand in the bridge is also influencial. Replacement of the methyl group with a phenyl increases the activity, whereas replacement with benzyl...

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