Tuning Sol Gel Phase Diagrams Of Doubly Thermosensitive Hydrophilic Diblock Copolymers In Water PDF Download

This dissertation presents the synthesis of stimuli-responsive hydrophilic diblock copolymers and the study of their behavior in water under various conditions. The polymers were made by "living"/controlled radical polymerization. Chapter 1 presents a background of this dissertation. Chapters 2-4 describe a family of doubly thermosensitive diblock copolymers with a small amount of carboxylic acid groups incorporated into either one or both blocks. The lower critical solution temperature (LCST) of the weak acid-containing block increases with increasing pH due to the ionization of carboxylic acid. Chapter 5 presents the preparation of pH-sensitive diblock copolymer micelle-embedded agarose hydrogels. Chapter 2 describes the synthesis and solution behavior of poly(methoxytri(ethylene glycol) acrylate-co-acrylic acid)-b-poly(ethoxydi(ethylene glycol) acrylate) (P(TEGMA-co-AA)-b-PDEGEA)). PTEGMA and PDEGEA are thermosensitive polymers with LCSTs of 58 and 9 °C [degree Celsius], respectively, in water. A 20 wt% aqueous solution of P(TEGMA-co-AA)-b-PDEGEA with pH of 3.11 underwent transitions from a free-flowing liquid, to a free-standing gel, to a hot liquid, and to a cloudy mixture upon heating. The Ts̳o̳l̳-̳g̳̳̳̳e̳̳l̳̳̳̳ [sol-to-gel transition temperature] and Tg̳̳̳̳e̳̳l̳̳̳̳-̳so̳l̳ [gel-to-sol transition temperature] are closely related to the LCSTs of the two blocks. Upon raising pH, the Tg̳̳̳̳e̳̳l̳̳̳̳-̳so̳l̳ increased, while the Ts̳o̳l̳-g̳̳̳̳e̳̳l̳̳̳̳ remained the same. Accordingly, only the upper boundary of the ̳so̳l̳-g̳̳̳̳e̳̳l̳̳̳̳ phase diagram shifted upward. Chapter 3 presents the tuning of Ts̳o̳l̳-g̳̳̳̳e̳̳l̳̳̳̳ of moderately concentrated aqueous solutions of doubly thermosensitive diblock copolymers by incorporating a small amount of AA groups into the lower LCST block and changing the solution pH. The AA content had a significant effect on the pH dependence of Ts̳o̳l̳-g̳̳̳̳e̳̳l̳̳̳̳-. Chapter 4 shows that by incorporating a small amount of carboxylic acid groups into both blocks of a doubly thermosensitive diblock copolymer, the C-shaped sol-gel phase diagram can be readily and reversibly shifted by changing the solution pH. Chapter 5 presents the fabrication of pH-sensitive diblock copolymer micelle-embedded agarose hydrogels. The gel properties were not significantly affected by the incorporation of the micelles even when the polymer concentration reached 5 mg/g. The pH-induced release of the payload from the core of micelles in a hybrid gel was studied. Chapter 6 presents conclusions and future work.