Temperature Variation Enables the Design of Biobased Block Copolymers via One-Step Anionic Copolymerization

A one-pot approach for the preparation of diblock copolymers consisting of polystyrene and polymyrcene blocks is described via a temperature-induced block copolymer (BCP) formation strategy. A monomer mixture of styrene and myrcene is employed. The unreactive nature of myrcene in a polar solvent (tetrahydrofuran) at -78 degrees C enables the sole formation of active polystyrene macroinitiators, while an increase of the temperature (-38 degrees C to room temperature) leads to poly(styrene-block-myrcene) formation due to polymerization of myrcene. Well-defined BCPs featuring molar masses in the range of 44-117.2 kg mol(-1)with dispersities,(sic), of 1.09-1.21, and polymyrcene volume fractions of 30-64% are accessible. Matrix assisted laser desorption ionization-time of flight mass spectrometry measurements reveal the temperature-controlled polymyrcene block formation, while both transmission electron microscopy and small-angle X-ray scattering measurements prove the presence of clearly microphase-separated, long range-ordered domains in the block copolymers. The temperature-controlled one-pot anionic block copolymerization approach may be general for other terpene-diene monomers.

Automated summary

The one-pot anionic block copolymerization approach controlled by temperature is applicable to other terpene-diene monomers. Temperature control enables the formation of polymyrcene blocks, with transmission electron microscopy and small-angle X-ray scattering measurements confirming the presence of clearly microphase-separated, long range-ordered domains in the block copolymers.