Deciphering the Triple-Peak C-O-C Stretching FTIR Absorbance Consistently Occurring in Semicrystalline PEG

Polyethylene glycol (PEG) is among the most intensively researched and applied polymers, exhibiting a very wide range of industrial, pharmaceutical, and biomedical applications. The strongest and most highly diagnostic absorbance in the FTIR spectrum of PEG and of PEG-containing polyurethanes, is the ether C-O-C stretching absorbance, which consistently appears as a triple-peak absorbance in a semicrystalline state. Surprisingly, this phenomenon has very seldom been mentioned or elaborated, and no direct structural diagnostic FTIR assignment has been determined for each component of the triple-peak. The present research conclusively demonstrates that the left-side and right-side components of the triple-peak are assigned to the chain-fold regions and the extended-chain regions of the crystallized chains, respectively, while the strong-wide central component is assigned to the randomly oriented chains in the amorphous phase of the semicrystalline PEG. The present demonstration was facilitated via the synthesis of a highly oriented fibrillar polyurethane block-copolymer, exclusively containing extended-chain-crystallized PEG soft-segments, obtained through dense hard-segment crosslinking under vigorous unidirectional shear-stress continuously applied during the synthesis. The present research results enable us to directly relate the FTIR spectra of PEG and block copolymers synthesized thereof, to their crystallization mechanisms and chain conformations, thus facilitating the development of improved industrial processing methods.