Synthesis and self-assembly of a novel amphiphilic diblock copolymer consisting of isotactic polystyrene and 1,4-trans-polybutadiene-graft-poly(ethylene oxide)

Abstract

Herein, a novel amphiphilic diblock copolymer consisting of isotactic polystyrene (iPS) and 1,4-trans-polybutadiene-graft-poly(ethylene oxide) (1,4-trans-PBD-g-PEO), iPS-b-(1,4-trans-PBD-g-PEO), was synthesized by the combination of living coordination copolymerization and graft copolymerization. iPS-b-1,4-trans-PBD was firstly synthesized via sequential monomer addition in the presence of 1,4-dithiabutandiyl-2,2′-bis(6-cumenyl-4-methylphenoxy) titanium dichloride (complex 1) activated by triisobutyl aluminum modified methylaluminoxane (MMAO). Moreover, hydroboration of double bonds in the 1,4-trans-PBD blocks were performed with 9-borabicyclo[3.3.1]nonane (9-BBN) and subsequent oxidation by NaOH/H₂O₂ to form hydroxyls. Consequently, PEO was grafted into the hydroxylated 1,4-trans-PBD block in terms of ring-opening polymerization of ethylene oxide with potassium/naphthalide as initiatior. We also described solvent-evaporation-induced self-assembly of iPS-b-1,4-trans-PBD in n-dodecane and iPS-b-1,4-trans-PBD-g-PEO in aqueous solution, which were selective solvent for 1,4-trans-PBD and for 1,4-trans-PBD-g-PEO blocks, respectively. In these cases, tetrahydrofuran (THF) was used as good and volatile solvent. These resultant iPS-containing diblock copolymers could self-assemble into spherical nano-micelles with an iPS core as amorphous agglomeration or a very low degree of crystallinity resulting from slow crystallization rate and nanoconfinement. In addition, after isothermal crystallization of iPS in the micellar cores self-assembled in n-dodecane at 120 °C for 3 hours, the micellar morphology changed from sphere-like to platelet-like. It was believed that isothermal crystallization of iPS induced the deformation of the micelles.