Metallocene Catalysts for 1‐Butene Polymerization

Summary: Isotactic polybutenes of variable isotacticity and melting points of form I in the range 100–125 °C have been prepared with both C 2 ‐ and C 1 ‐symmetric zirconocenes. The C 1 ‐symmetric zirconocenes bearing the bilateral symmetric 2,5‐dimethyl‐7 H ‐cyclopenta[1,2‐b:4,3‐b′]dithiophene ligand connected by a dimethylsilandiyl bridge to a substituted indenyl ligand produce iPB with higher molecular mass, up to 400 000 at polymerization temperature of 70 °C in liquid butene. The degree of isotacticity depends on the substitution pattern of the indenyl ligand. The correlations between microstructure and melting points of the crystalline forms I and II of iPB have been defined. Some relevant differences in catalyst selectivity between propylene and 1‐butene polymerizations have been identified.Linear correlation of melting points of form I and form II in isotactic poly(1‐butene)s of different chain regularities.