Multiple Sol-Gel Transitions of PEG-PCL-PEG Triblock Copolymer Aqueous Solution

An aqueous solution of a poly(ethylene glycol)‐polycaprolactone‐poly(ethylene glycol) (PEG‐PCL‐PEG) with a composition of EG13CL23EG13 undergoes multiple transitions, from sol‐to‐gel (hard gel)‐to‐sol‐to‐gel (soft gel)‐to‐sol, in the concentration range 20.0∼35.0 wt.‐%. Through dynamic mechanical analysis, UV‐vis spectrophotometry, small angle X‐ray scattering, differential scanning calorimetry, microcalorimetry and 13C NMR spectroscopy, the mechanism of these transitions was investigated. The hard gel and soft gel are distinguished by the crystalline and amorphous state of the PCL. The extent of PEG dehydration and the molecular motion of each block also played a critical role in the multiple transitions. This paper suggests a new mechanism for these multiple transitions driven by temperature changes. An aqueous solution of EG13CL23EG13 undergoes sol‐to‐gel (hard gel)‐to‐sol‐to‐gel (soft gel)‐to‐sol multiple transitions, where the hard gel and soft gel are distinguished by crystalline and amorphous state of the PCL. The mechanism of transitions and molecular characteristics in each phase are investigated.