Ziegler–Natta Catalyst - Stereochemistry of Poly-1-alkenes

Stereochemistry of Poly-1-alkenes

Natta used first polymerization catalysts based on titanium chlorides to polymerize propylene and other 1-alkenes. He discovered that these polymers are crystalline materials and ascribed their crystallinity to a special feature of the polymer structure called stereoregularity.

The concept of stereoregularity in polymer chains is illustrated in the picture above with polypropylene. Stereoregular poly(1-alkene) can be isotactic or syndiotactic depending on the relative orientation of the alkyl groups in polymer chains consisting of units −−, like the CH₃ groups in the figure. In the isotactic polymers, all stereogenic centers CHR share the same configuration. The stereogenic centers in syndiotactic polymers alternate their relative configuration. A polymer that lacks any regular arrangement in the position of its alkyl substituents (R) is called atactic. Both isotactic and syndiotactic polypropylene are crystalline, whereas atactic polypropylene, which can also be prepared with special Ziegler–Natta catalysts, is amorphous. The stereoregularity of the polymer is determined by the catalyst used to prepare it.