Association and physical gelation of ABA triblock copolymer in selective solvent

✍ Scribed by Katsuhiro Inomata; Daisuke Nakanishi; Ai Banno; Eiji Nakanishi; Yosuke Abe; Ryuta Kurihara; Kentaro Fujimoto; Takuhei Nose

• Publisher: Elsevier Science
• Year: 2003
• Tongue: English
• Weight: 291 KB
• Volume: 44
• Category: Article
• ISSN: 0032-3861
• DOI: 10.1016/s0032-3861(03)00534-2

✦ Synopsis

Association behavior and physical gelation mechanism of ABA triblock copolymer dissolved in B-selective solvent have been studied systematically from dilute to moderately concentrated solutions. Static and dynamic light scattering and nuclear magnetic resonance measurements for dilute solutions of poly(methyl methacrylate)-block-poly(tert-butyl acrylate)-block-poly(methyl methacrylate) (PMMA -Pt BuA -PMMA) in 1-butanol (Pt BuA selective solvent) indicated that PMMA-Pt BuA -PMMA chains are molecularly dissolved above 50 8C. With decreasing temperature, the triblock copolymers form associated micelles consisting PMMA associated core and Pt BuA shell. Linear dynamic viscoelastic measurements for solutions with moderate concentration (3.9-12.0 wt%) revealed that the system was viscous sol state at 60 8C. Drastic increase of shear storage modulus ðG 0 Þ occurred with decreasing temperature, and at 25 8C, G 0 showed rubbery plateau with weak frequency dependency, means the formation of elastic physical gel. The consistency between the temperature for micelle formation and that at the increase in G 0 indicates that the physical gelation is owing to the network formation as the result of the association of PMMA chains and the bridging Pt BuA chains connecting the PMMA cores. Master curves for the dynamic moduli were derived by timetemperature superposition along the frequency axis. Just above sol -gel transition concentration ðC gel Þ; the master curves suggest the existence of fairy amount of aggregate that is not incorporated in the macroscopic network. With the increase in polymer concentration, the master curves become to reveal Maxwell-type viscoelasticity with narrow relaxation time distribution, suggesting the formation of transient network with easily generation and destruction of crosslinks. Concentration dependency of the plateau modulus is stronger than the theoretically expected, means the macroscopic transient network grows with polymer concentration by increasing the fraction of elastically effective bridging Pt BuA chain above C gel :