The cationic polymerizations of α and β pinenes and limonene were compared

and the possibility of living polymerization of the three monomers was also examined. With Lewis acid AlCl 3 catalyst

the polymerization rate decreased in the following order: β pinene>limonene> α pinene. The addition of SbCl 3 accelerated the polymerizations of α pinene and limonene

and retarded the polymerization of β pinene. In contrast to the polymerizations with AlCl3

the polymerization of α-pinene and limonene

and retarded the polymerization of β-pinene.In contrast to the polymerizations with AlCl3

the polymerization of α-pinene was faster than that of limonene when catalyzed with AlCl3/SbCl3.As compared with the AlCl3 catalyst

AlCl3/SbCl3 binary system gave polymers of α-pinene with higher molecular weight

polymers of limonene with similar molecular weight

and polymers of β-pinene with lower molecular weight.In contrast to the structure of α-pinene polymer

the structures of β-pinene and limonene polymers were not affected by the addition of SbCl3.The living polymerization of reactive β-pinene monomer could be achieved with Styrene-HCl adduct/TiCl3(OiPr) initiating system

however

attempts of the living polymerizations of α-pinene and limonene with a series initiating system failed because of the low monomer reactivity.