STEREOCONTROLLED POLYMERIZATION OF DIENE MONOMERS WITHIN A TRIS(O-PHENYLENEDIOXY)CYCLOTRIPHOSPHAZENE TUNNEL CLATHRATE

The inclusion and polymerization of the diene monomers 2,3-dimethylbut adiene, isoprene, trans-piperylene, trans-2-methyl-1,3-pentadiene, 4-m ethyl-1,3-pentadiene, chloroprene, 1,3-cyclohexadiene, 2,3-dimethylbut adiene/isoprene, isoprene/trans-piperylene, and isoprene/butadiene wit hin the tunnels of clathrates formed by tris(o-phenylenedioxy)cyclotri phosphazene have been achieved. The polymerizations were accomplished by Co-60 gamma-irradiation. All the polymers obtained by this techniqu e resulted from 1,4-addition. Specifically, 1,4-trans-poly(dimethylbut adiene), 1,4-trans-poly(isoprene), isotactic 1,4-trans-poly(trans-pipe rylene), isotactic 1,4-trans-poly(trans-2-methyl-1,3-pentadiene), 1,4- trans-poly(4-methyl-1,3-pentadiene), 1,4-trans-poly(chloroprene), atac tic 1,4-poly(cyclohexadiene), 1,4-trans-poly(isoprene/dimethyl-butadie ne), 1,4-trans-poly(isoprene/trans-piperylene), and 1,4-trans-poly(iso prene/butadiene) were formed. The stereoregularity is explained in ter ms of monomer packing arrangements in the tunnels.