NAPHTHALENE CHEMISTRY - 2. A NOVEL ROUTE FOR THE SYNTHESIS OF WELL DEFINED STAR BLOCK COPOLYMERS DISPLAYING AN A(B)//2 ARCHITECTURE FROM HYDROCARBON MONOMERS (A) AND ETHYLENE OXIDE (B).

In the reported experiments star block copolymers were obtained by graft copolymerization of ethylene oxide onto polystyrene (PST), polymethylstyrene (P alpha MS), poly p-tert butyl-styrene (PTBS) and polyisoprene (PIP). Experimental data are presented which demonstrate that a naphthalene group can be successfully attached to the end of ″living″ polymer chains (PST, PTBS, PIP) by reaction of the corresponding polymeric Grigant compound with beta -bromomethylnaphthalene. When it is attached to the end of the PIP chain, the metallation proceeds similarly as beta -ethylnaphthalene. While to the end of PST or PTBS, the naphthalene end group is released. The results are confirmed by UV spectra carbanions titration and hydrolyzed products. In the case of dianion of naphthalene ended a PIP or PST-PIP or PTBS-PIP, an A(B)//2 well defined star block copolymer can be obtained in high yield.