Abstract:
The invention is a process for the preparation of tapered block copolymers according to one of the formulae: B-t-A or A-B-t-A, wherein A comprises a polymer block derived from one or more monovinylidene aromatic monomers, B comprises a polymer block derived from one or more conjugated dienes, and t is a tapered polymer block derived from one or more monovinylidene aromatic monomers and one or more conjugated dienes wherein the portion of the block closest to block A is rich in monovinylidene aromatic monomer units, the portion of the block closest to block B is rich in conjugated diene units and the relative amount of conjugates diene and monovinylidene aromatic monomer units gradually changes along the backbone of the tapered block, comprising: a) contacting one or more conjugated dienes with a monofunctional lithium alkyl initiator or a polymer block derived from monovinylidene aromatic monomers with a terminal living lithium anion capable of initiating anionic polymerization and a hydrocarbon solvent, in a closed reactor equipped with a reflux condenser under conditions of reflux; b) partially polymerizing the one or more conjugated dienes; and c) after step b), contacting with the reaction mixture one or more monovinylidene aromatic monomers under conditions such that the unreacted conjugated diene and monovinylidene monomers polymerize; wherein the materials condensed during the process are recycled to the reactor.