Architectural control of polystyrene physical properties using branched anionic polymerization initiated at ambient temperature

Abstract Ambient temperature‐initiated anionic polymerization has generated branched polystyrenes of varying molecular weights and architectures by inclusion of a distyryl branching comonomer into a conventional sec ‐Butylithium‐initiated polymerization of styrene. Primary chain length control within the branched polymers, and restriction of the branching points to varying segments of the primary chains, led to variations of glass transition temperature with no direct correlation to the branched polymer molecular weight but a strong relationship to the length of individual chains comprising the branched macromolecules.