Thermo-associating polymers based on cross-linked 2-acrylamido-methylpropane sulfonic acid, part B: Effect of co-solutes on solution behavior

Abstract

Thermo-thickening copolymers have gained prominence in technological advancements due to its attractive properties and great potential to overcome the deficiency of viscosity of conventional copolymer upon increasing temperature and salinity. The work in this paper was devoted to examine the aqueous solution viscosity behavior of a new class thermo-thickening copolymer, poly(sodium 2-acrylamido-2-methylpropanesulfonic acid-co-N,N’-methylenebisacrylamide)-g-poly(acrylamide-co-N, N’-diethylacrylamide) denoted as CGBA in the presence of co-solutes. CGBA, which were reported in our previous work manifested notable viscosity enhancement macroscopically above the threshold temperature. However, the effect of small molecules on thermo-associative behavior was still unsettled. Based on structure/properties dependence of CGBA, this work aimed to explore the effect of small molecules and the role of molecular structure on aqueous solution viscosity behavior. The contributions of various added co-solutes such as anionic surfactant, acidic specie, monovalent and divalent salts were considered. For that purpose, three copolymers having distinctive composition of side-arms and length of side-arms were selected and their thermo-associating behaviors were followed by viscosity measurement. Results from rheological tests showed that these co-solutes induced notable modifications in the characteristic of thermo-thickening behavior. For all the co-solutes used, it was observed a strong dependence between the side-arms/water/co-solutes ternary system and the macroscopic property upon heating. Spectrofluorimetric and environmental scanning electron microscope (ESEM) tests were used to gain a deeper insight into the precise mechanism of phase transition process. Results from spectrofluorimetric experiment indicated that, only when the fraction of DEAm in CGBA was higher enough, it would appear strong abrupt macroscopic property above the threshold temperature, which could delay the offset of hydrophobic association phenomenon in the presence of anionic surfactant. Similar effect was also observed in the presence of added acidic specie. Conversely, the addition of monovalent and divalent salts showed dissimilar effects. ESEM revealed that, in comparison with monovalent salt, divalent salt favored the formation of larger and more condensed CGBA skeleton above the threshold temperature which led to an improved macroscopic response. This work demonstrates for the first time the micro-structure changes of copolymer, which was probably the main reason for the changes in magnitude of thermo-thickening effect in different divalent salt dosages.