Macromolecules, Vol.44, No.9, 3556-3566, 2011
Tuning of Thermo-Triggered Gel-to-Sol Transition of Aqueous Solution of Multi-Responsive Diblock Copolymer Poly(methoxytri(ethylene glycol) acrylate-co-acrylic acid)-b-poly(ethoxydi(ethylene glycol) acrylate)
This article reports on the synthesis of a hydrophilic diblock copolymer composed of two distinct thermosensitive polymers with one block containing a small amount of carboxylic acid groups, poly(methoxytri(ethylene glycol) acrylate-co-acrylic acid)-b-poly(ethoxydi(ethylene glycol) acrylate) (P(TEGMA-co-AA)-b-PDEGEA), and the study of thermo-induced sol-gel-sol transitions of its moderately concentrated aqueous solutions at various pH values, The diblock copolymer was obtained by the removal of tert-butyl groups of P(TEGMA-co-tert-butyl acrylate)-b-PDEGEA, which was synthesized by reversible addition-fragmentation chain transfer polymerization. PTEGMA and PDEGEA are thermosensitive polymers with lower critical solution temperatures (LCSTs) of 58 and 9 degrees C, respectively, in water. The incorporation of a small amount of carboxylic acid groups into PTEGMA allowed the LCST of the P(TEGMA-co-AA) block to be tuned by changing the solution pH. We found that a 20 wt % aqueous solution of P(TEGMA-co-AA)-b-PDEGEA with pH of 3.11 (measured at 0 degrees C) underwent multiple phase transitions upon heating, from a clear, free-flowing liquid (< 19 degrees C) to a clear, free-standing gel (19 to 39 degrees C), to a clear, free-flowing hot liquid (40 to 55 degrees C), and to a cloudy mixture (>= 56 degrees C). With the increase of pH, the gel-to-sol transition (Tgel-sol) and the clouding temperature (T-clouding) of the sample shifted to higher values, while the sol-to-gel transition temperature (Tsol-gel) remained the same. These transitions and the tunability of Tgel-sol stemmed from the thermosensitive properties of the two blocks of the diblock copolymer and the pH dependence of the LCST of P(TEGMA-co-AA), which was confirmed by differential scanning calorimetry and dynamic light scattering studies. Using the vial inversion test method, we further mapped out the C-shaped sol-gel phase diagrams of (PTEGMA-co-AA)-b-PDEGEA in water in the moderate concentration range at three different pH values (3.11, 4.49, and 5.25, all measured at 0 degrees C). While the lower temperature boundaries overlapped, the upper temperature boundary shifted upward and the critical gelation concentration decreased with the increase of pH. In contrast, the sol-gel phase diagram of PTEGMA-b-PDEGEA, which contained no pH-responsive groups, showed no changes in Tsol-gel, Tgel-sol, and T-clouding with pH.