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These catalysts were discovered in the 1950s by Karl Ziegler, who used a mixture of the above compounds to catalyse the polymerisation of ethylene. Giulio Natta, using the same mixture to catalyse propylene, discovered that the process gave a stereoregular polymer, that is, one with a regular arrangement of side chains.
This stereoregularity is believed to follow from a polymer growth mechanism known as the Cossee-Arlman mechanism, in which the polymer grows at vacant Cl sites at the Ti surface. In the search for a deeper understanding and control of Ziegler-Natta polymerisation at the molecular level, a number of metallocene catalysts have been developed, often offering fine control over the composition and tacticity of the polymer chain so produced.