Abstract

At the initial stages the polymerization of cis-cyclooctene in the bulk with the catalysts Me3C-CH=Mo(NAr)(OCMe2CP3)2, PhMe2C-CH=Mo(NAr)(OCMe2CP3)2, Me3Si-CH=Mo(NAr)(OCMe2CP3)2, and PhMe2Si-CH=Mo(NAr)(OCMe2CP3)2 predominantly affords cis-polyoctenamers. The content of the trans- units in the polymer increases with an increase in the conversion. The sharpest increase in the trans- unit content observed for conversions higher than 80% is related to secondary metathesis reactions. The number-average molecular weights of the polymers increase linearly with the conversion. At conversions above 80% the molecular weights decrease due to the increasing contribution of chain transfer reactions. Polyoctenamers with the increased content of trans- units crystallize in two modifications.

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