Abstract
Polyether based side-chain liquid crystalline (SCLC) copolymers with distinct microstructures were prepared using living anionic polymerization techniques. The composition, end groups, purity, and sequence of the resulting copolymers were elucidated by matrix-assisted laser desorption/ionization mass spectrometry (MALDI-MS) and tandem mass spectrometry (MS/MS). MALDI-MS analysis confirmed the presence of (CH3)3CO– and –H end groups at the initiating (α) and terminating (ω) chain end, respectively, and allowed determination of the molecular weight distribution and comonomer content of the copolymers. The comonomer positions along the polymer chain were identified by MS/MS, from the fragments formed via C–O and C–C bond cleavages in the polyether backbone. Random and block architectures could readily be distinguished by the contiguous fragment series formed in these reactions. Notably, backbone C–C bond scission was promoted by a radical formed via initial C–O bond cleavage in the mesogenic side chain. This result documents the ability of a properly substituted side chain to induce sequence indicative bond cleavages in the polyether backbone.
Highlights
Side-chain liquid crystalline (SCLC) polymers and copolymers are used in numerous technological applications, such as sensing, transistors, optics, and optical data storage [1,2,3,4]
Recent studies have further documented that properly structured SCLC polymers can undergo reversible shape changes in response to external stimuli, like heat, light, or humidity, such controlled deformability is desired for the design and engineering of microactuators and soft robots [5,6,7]
These important important structural structural features features could could be conclusively determined by MALDI-MS
Summary
Side-chain liquid crystalline (SCLC) polymers and copolymers are used in numerous technological applications, such as sensing, transistors, optics, and optical data storage [1,2,3,4]. The mesogenic (i.e., liquid crystalline) side chains endow optical anisotropy, a valuable property in optical devices. Recent studies have further documented that properly structured SCLC polymers can undergo reversible shape changes in response to external stimuli, like heat, light, or humidity, such controlled deformability is desired for the design and engineering of microactuators and soft robots [5,6,7]. The mentioned utilitarian applications have spurred significant progress in the synthesis of SCLC (co)polymers with low polydispersity (Ð), controlled chain length and chain end functionalities, and no or low amounts of byproducts [2,3,4,5,6,7]
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