| The goal of this dissertation is to understand from first principles the structure-rheology relation of telechelic associative polymers, which are popular as rheology modifiers in a lot of industrial products.; From the molecular structure and the surface tension data of the telechelic polymers and the solvent, we can predict the aggregation number and the radius of the micelles formed in aqueous solutions, which are key parameters that determine the pair potential. The distribution of the aggregation number is proven to be broad, consistent with experiments from various techniques.; To quantify the pair potential between micelles, the interactions between planar brushes are examined. By allowing the layers to relax while bridges form, we obtain a free energy lower than that of Milner and Witten's prediction. Converting the planar potential to spherical geometry by Derjaguin approximation leads to the pair potential between micelles, from which the second virial coefficient in osmotic pressure and high frequency modulus scaled on the radius and volume fraction of micelles are predicted.; Comparing our predictions with experiments shows good consistency. The number and weight average aggregation numbers agree well with the fluorescence and static light/neutron scattering results, whereas the complicated average radius derived from the principles of the techniques agrees with the hydrodynamic radius from dynamic light scattering. The predicted attractive virial coefficient is consistent with that deduced from the phase diagram and dynamic light scattering. The high frequency modulus shows a systematic deviation from the experiments, possibly due to hydrodynamic interactions not accounted for in the calculation.; In conclusion, with our theories, we can indeed predict the structure, interactions and rheology of a family of telechelic associative polymers in solutions, which compare well with available data by us and from literature. |
