Ring-opening metathesis polymerization of cyclodecadien derivatives

Abstract

Various substituted cyclodecadienes, methyl (Z,E or E,Z)-3,7-cyclodeca-dienylcarboxylate, (Z,E or E,Z)-3,7-cyclodecadien-1-carboxylic acid, (Z,E or E,Z)-3,7-cyclodecadienylmethanol, and 8- or 9-methyl-(Z,E)-1,5-cyclodecadiene were prepared and their polymerization were carried out with several catalyst systems. Those four cyclodecadiene derivatives exhibited quite different polymerization behaviors depending upon the catalyst systems employed, reaction temperature, and reaction time. Methyl (Z,E or E, Z)-3,7-cyclodecadienylcarboxylate underwent ring-opening metatheses polymerization by $WCl_4(O-2,6-C_6H_6X_2)_2$ (X=Ph,Me,Cl)/$PbEt_4$. IR and NMR spectra of monomers and polymers confirmed that the resulting polymers had the structure in that methyl acrylate and butadiene were incorporated by 1 to 2 ratio in alternating fashion. In the polymerization of (Z,E or E,Z)-3,7-cyclodecadien-1-carboxylic acid, the successful ring-opening polymerization could be achieved with $WCl_6/Et_3Al$ and $MoCl_5/Et_3Al$. The resulting polymer was powdery and was insoluble in common organec solvents such as chlorform, benzene and acetone, but soluble in trifluoroacetic acid. (Z,E or E,Z)-3,7-Cyclodecadienylmethanol was also prepared and subjected to polymerization, but the polymerizatino did not proceed to notable extent. Polymerization, of 8- or 9-methyl-(Z,E)-1,5-cyclodecadiene was carried out with $WCl_6/EtAlCl_2$ and $WCl_4(O-2,6-C_6H_3Ph_2)_2/PbEt_4$. Small extent of addition product was incorporated into the resultiog polymers obtained from the polymerization by $WCl_6/EtAlCl_2$. This resulat was attributed to the acidic properties of $EtAlCl_2$. However, the polymer obtained from the polymerization carried out with $WCl_4(O-2,6-C_6H_3Ph_2)_2/PbEt_4$ was free of vinylic addition procuct.