Ethylene copolymerization with 1,3‐cyclohexadiene (CHD) was investigated by using methylaluminoxane (MAO) activated single‐site catalysts including bridged and non‐bridged titanium half‐sandwich and bimetallic cobalt(I) complexes. MAO activated CpTiCl2[NP(tBu)3] (Cp = cyclopentadienyl, tBu = tert‐butyl) gave high molecular weight CHD copolymers without encountering catalyst activity losses. According to the NMR microstructure investigation the resulting copolymers are highly regioregular.
Vinyl‐terminated isotactic polystyrene macromonomers were copolymerized with ethylene and 1‐octene to new polyolefin graft copolymers with crystallizable polystyrene side chains. The iPS content was varied from 4 to 78 wt.‐% using different metallocene and halfsandwich catalysts. No solubility problems of the stereoregular macromonomer occured, because iPS does not crystallize during polymerization. In addition the polymers show nanophase separation of the polyolefin backbone and the iPS side chains. The crystallization of iPS, having a melting point of about 200 °C, can be achieved by annealing. This synthesis strategy allows the fabrication of a new class of thermoplastic elastomers with improved heat distortion temperatures.magnified image
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