Method for preparing coupled asymmetric polymers

A process for preparing a coupled asymmetric block copolymer of a vinyl aromatic hydrocarbon and a conjugated diene which comprises: (a) adding sufficient anionic polymerization initiator to the vinyl aromatic hydrocarbon monomer to start polymerization of the vinyl aromatic hydrocarbon, (b) polymerizing the vinyl aromatic hydrocarbon for a time sufficient to form a first set of vinyl aromatic hydrocarbon blocks having a desired molecular weight, (c) adding sufficient anionic polymerization initiator to start polymerization of a second set of vinyl aromatic hydrocarbon blocks, (d) completing the polymerization of the vinyl aromatic hydrocarbon for a time such that the first set of vinyl aromatic hydrocarbon blocks continues to grow to the desired molecular weight and the second set of vinyl aromatic hydrocarbon blocks grows to a desired smaller molecular weight, (e) adding a conjugated diene and polymerizing it on the ends of the vinyl aromatic hydrocarbon blocks for a time sufficient to form vinyl aromatic hydrocarbon-conjugated diene arms of the desired molecular weight, and (f) adding a coupling agent and coupling the arms to form the asymmetric block copolymer.