| Summary: | We demonstrate the successful synthesis of linear and non-linear star block copolymers consisting of the highly segregated polystyrene (PS) and poly(dimethylsiloxane) (PDMS) blocks through sequential anionic polymerization combined with chlorosilane chemistry. To study the macromolecular architecture effect on the adopted morphology star block copolymers with six equivalent diblock arms [(PS-b-PDMS)6] were synthesized and compared with their linear diblock copolymer precursors as well as with the corresponding star block copolymers with smaller arm number (2, 3, 4) but identical molecular characteristics. After verifying the molecular and thermal characteristics, bulk studies were carried out through transmission electron microscopy and small angle X-ray scattering. Well-defined structures with enhanced order and similar domain spacing values, irrespective of the architecture complexity of the samples, were observed. The better order of star block copolymers suggests an alternative way to further reduce the lower limit of repeating period by tuning the architecture which is important for the potential future use of the copolymers for nanotechnology related applications. The findings of the specific study are related to the effects of the increased conformational restriction of the inner block. Herein, we show morphological transformations in the (PS-b-PDMS)6 copolymers having non symmetric volume fraction ratios when compared to their linear diblock precursors and triblock copolymers which has not been observed in previous relevant (PS-b-PDMS)n studies that involved stars with less than six arms. To establish the structure/property relationship as a function of arm number, a series of samples involving the diblock precursor, the triblock, the three-, four- and six- arm star block copolymers was prepared, and a systematic comparison was conducted.
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