Polymerization of norbornene by modified Ziegler‐catalysts

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Abstract
For the polymerization of norbornene, three modes of reaction have been known: vinyl polymerization (I) and ring‐opening polymerizations giving trans (II) and cis (III) double bonds.In the present study, the polymerization by modified ZIEGLER type catalysts was carried out. Modification was obtained by the addition of several LEWIS base compounds as the third component to the binary system of metal alkyl and titanium tetrachloride. The AlEt3/TiCl4 (2.5/1), AlEt3/TiCl4 (1/1), and LiAlEt3Bu/TiCl4 (2.5/1) systems induce the norbornene polymerization giving polymers consisting mostly of the units (I) + (II), (I) and (II), respectively. These three systems were transformed by the addition of some LEWIS bases into the species which give high molecular weight polymers consisting exclusively of the ring‐opened units (II) and (III). The modification by LEWIS base is prominent in the region of the base/TiCl4 ratio of 2 to 4.

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