Compatibilization of Polystyrene/Poly(dimethylsiloxane) using Star Polymers Containing a gamma-Cyclodextrin Core and Polystyrene Arms.

Abstract

Star polymers containing a γ-cyclodextrin (CD) core and polystyrene (PS) arms (CD-star) were successfully synthesized by atom transfer radical polymerization. These stars are the first of their kind containing a γ-CD core. CD-stars made with twelve PS arms proved to be soluble in typical PS solvents. Control over CD-star arm length was achieved, as shown by nuclear magnetic resonance (NMR) and gel permeation chromatography (GPC) analysis.

Rapidly stirred blends of polydimethylsiloxane (PDMS) and PS prepared in chloroform with and without CD-star formed an emulsion. Adding CD-star to these turbid solutions resulted in clearing, whereas control solutions without CD-star remained turbid. Post-stirring, these clear solutions demonstrated excellent temporal stability illustrating their successful compatibilization. Characterization of these clear solutions by 2D-NMR revealed that CD-stars were threaded onto PDMS. This complexation formed a hybrid slip-ring copolymer with PDMS as the backbone and CD-star PS arms effectively acting as the grafts. Solution characterization via capillary viscometery, dynamic light scattering, and GPC showed traits similar to traditional graft copolymers.

Films were made from the blended solutions by spin or solution casting. Spun-cast films prepared from compatibilized solutions exhibited homogeneous nanophase morphology, whereas non-compatibilized solutions displayed heterogeneous microphase morphology. Atomic force microscopy and scanning electron microscopy analyses of these films revealed PDMS phase domains measuring 50nm or less. However, solution cast films with subsequent compression molding showed macroscopic phase segregation for samples with or without CD-star. Significant loss of PDMS was observed during processing. Compositional analysis conducted by 1H-NMR revealed ~80% PDMS retention for films with CD-star, whereas only ~20% retention was observed for films without CD-star. This larger PDMS retention for samples with CD-star results from the anchoring of PDMS chains which threaded through CD-stars. Differential scanning calorimetry and dynamic mechanical analysis characterization point to partial compatibilization, as determined from the glass-transition temperatures of the homopolymers shifting toward each other. Solution-cast film characterization by thermal gravimetric analysis confirmed the PDMS thermal degradation decreased with increased CD-star complexation.