ω‐Chloro‐α‐olefins as co‐ and termonomers for the synthesis of functional polyolefins

This paper deals with the use of ω‐chloro‐α‐olefins as monomers for the synthesis of chloro‐functional homo‐, co‐ and terpolyolefins in the presence of (IVb) metallocene/MAO catalytic systems. Two ω‐chloro‐α‐olefins, 11‐chloroundec‐1‐ene and 5‐chloropent‐1‐ene, were tested. It was found that only the functional olefin containing the longer aliphatic spacer between the alkene function and the halide polymerizes readily in the presence of the rac‐Et(Ind)2ZrCl2/MAO catalyst. The drastic influence of the reaction solvent on the chloro‐olefin reactivity and (co)polymerization behavior is examined and discussed. Finally, the terpolymerization of 11‐chloroundec‐1‐ene with ethylene and propene is investigated. In a second part, the quantitative preparation, by derivatization of 11‐chloroundec‐1‐ene units, of functional polyolefins bearing benzoate, hydroxy or azido functions as side groups is described. The corresponding functional polymers are characterized by IR and 1H NMR spectroscopy.