Novel supramolecular block copolymer containing organic–inorganic pentablock copolymer by ATRP of styrene and vinyl acetate using polydimethylsiloxane/cyclodextrin inclusion complexes as macroinitiator

Organic–inorganic pentablock copolymers have been synthesized via atom transfer radical polymerization (ATRP) of styrene (St) and vinyl acetate (VAc) monomers at 60 °C using CuCl/N,N,N′,N″,N″-pentamethyldiethylenetriamine as a catalyst system initiated from boromoalkyl-terminated poly(dimethylsiloxane) (PDMS)/cyclodextrins macroinitiator (Br-PDMS/γ-CD). Br-PDMS-Br was reacted with γ-CD in different conditions with inclusion complexes being characterized through hydrogen nuclear magnetic resonance (¹H NMR) and differential scanning calorimetry (DSC). Resulting Br-PDMS-Br/γ-CD inclusion complexes were taken as macroinitiators for ATRP of St and VAc. Well-defined poly(styrene)-b-poly(vinyl acetate)-b-poly(dimethylsiloxane/γ-cyclodextrin)-b-poly(vinyl acetate)-b-poly(styrene) (PSt-b-PVAc-b-PDMS/γ-CD-b-PVAc-b-PSt) pentablock copolymer was characterized by ¹H NMR, gel permeation chromatograph (GPC) and DSC. There was a good agreement between the number-average molecular weight calculated from ¹H NMR spectra and that of theoretically calculated. Pentablock copolymers consisting of Br-PDMS-Br/γ-CD inclusion complex as central blocks (inorganic block) and PVAc and PSt as terminal blocks were synthesized by this technique. PSt-b-PVAc-b-PDMS/γ-CD-b-PVAc-b-PSt pentablock copolymer can undergo a temperature-induced reversible transition upon heating of the copolymer complex from white complex at 22 °C to green complex in 55 °C which characterized with XRD and ¹H NMR. XRD showed a change in crystallinity percent of St peak with changing the temperature which calculated by Origin75 software.