Synthesis of Organic/Inorganic Hybrid Quatrefoil-Shaped Star-Cyclic Polymer Containing a Polyhedral Oligomeric Silsesquioxane Core

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We report the synthesis of quatrefoil-shaped star-cyclic polystyrene, star-cyclic PS, containing a polyhedral oligomeric silsesquioxane (POSS) core via the combination of atom transfer radical polymerization (ATRP) and click chemistry techniques. The obtained star-cyclic PS represents a new chain topology in the category of nonlinear-shaped polymers. Using octa(3-chloropropyl) polyhedral oligomeric silsesquioxane, POSS-( Cl ) 8, as the starting material, its azidation and subsequent click reaction with a slight excess of propargyl 2-bromobutyrate afforded octafunctional initiator, POSS-( Br ) 8 . 8-arm star-linear PS- N 3 was obtained by the azidation of star-linear PS- Br, which was synthesized by the ATRP of styrene using POSS-( Br ) 8 as the initiator. Model reaction between α,ω-diazido-terminated PS ( N 3 -PS- N 3 ) and difunctional propargyl ether confirmed that bimolecular click cyclization reaction can effectively occur under highly dilute conditions. Next, intramolecular click ring closure of star-linear PS- N 3 was conducted under highly dilute conditions, using propargyl ether as the difunctional linker and CuBr/PMDETA as the catalyst, affording quatrefoil-shaped star-cyclic PS. Gel permeation chromatography (GPC), 1 H NMR, and FT-IR analysis confirmed the complete consumption of azide moieties in star-linear PS- N 3 and that the coupling reaction proceeded via the intramolecular manner. Differential scanning calorimetry (DSC) results revealed that star-cyclic PS possesses higher glass transition temperature ( T g ) than that of star-linear PS, possibly due to the ring topology of PS arms in the former.