Lin Fu1, Xuhong Guo2, Stephen Lincoln3, and Robert Prudhomme1. (1) Princeton University, Princeton, NJ, (2) East China University of Science and Technology, Shanghai, China, (3) University of Adelaide, Australia
Water soluble associative polymers, which are usually composed of hydrophilic backbones and hydrophobic side chains, are widely used as rheology modifiers in coating, painting, cosmetics and pharmaceutics. In this study, a novel associative polymer network with tunable rheological properties is developed based on cyclodextrin-hydrophobe inclusion complex. Mixtures of two polyacrylic acid backbone polymers: cyclodextrin attached to PAA and hydrophobically modified PAA are used. With cyclodextrin host-guest inclusion as the associative sites, this novel polymer network is able to provide more controllable rheological properties than traditional associative polymers, because: first, the lifetime of this host-guest association can be well controlled by the length of alkyl chain inserted into the cyclodextrin; second, the binary nature of cyclodextrin-hydrophobe inclusion prevents hydrophobes from multiple association. At the same time, this system can serve as a model associative polymer network for understanding polymer association theory. Dynamic rheological properties of this mixture solution can be quantitatively controlled by adding free cyclodextrin or sodium dodecylsulfate (SDS). Dynamic modulus could change up to several orders of magnitude, even from gel state to sol state. The phase behavior of this mixture solution is experimentally studied by turbidity measurement and rheological approach. The thermodynamic behavior is found to show good consistency with associative gelation theory. Further, we studied the life time of cyclodextrin-hydrophobe interaction independently from isothermal titration calorimeter and surface plasmon resonance study. Both thermodynamics and dynamics of this cyclodextrin inclusion process are explored for better controlling rheological properties of this model system.