Dye Clicked Thermoplastic Polyurethane as a Generic Platform toward Chromic-Polymer Applications

Abstract

Chromic dyes responding against external stimuli are useful in various field of applications especially to colorimetric sensors. However, there have been several limitations in generic application because of its cost, stability and reliability. Here, we introduced highly functionalizable polymeric materials as a supporter covalently modified with controlled amount of chromic dyes. The photochromic organic dye (spiropyran) and highly functional thermoplastic polyurethanes (TPU) have been adopted as a representative example. Conventional polymeric solution processes such as film processing, wet-spinning, electrospinning and ink-writing are readily applicable because dye-TPU maintains its own solubility in various organic solvents. Additionally, since the concentration of dye on TPU are precisely controllable, these dye-TPU solution can be adopted in broad range of specific applications, such as secret coding, smart fabric, and chromic polymeric film layer.

Mechanochemical tools for polymer materials

“…Another class of polymers that are well studied in polymer mechanochemistry are poly(urethanes) (PU), because of their highly-tunable properties. 43,50,74,92,104,[148][149][150][151][152][153][154][155][156][157][158][159][160] Their synthesis is based on a Process in solution PMA, 35,56,62,63,67,84,[137][138][139][140][141][142] PMMA, 143 PEA, 144 PnBA, 144 PiBA, 144 PtBA, 144 PS, 145,167 copolymers, 167,168,171 PCL, 146,147 polybutadiene 68,123,170 Controlled/living polym. (SET-LRP, ATRP, ROP, ROMP, RAFT, etc.. .…”

“…Bifunctional mechanophore used as an initiator Well-defined polymers with controlled molar masses (9-300 kDa), tunable architectures, low dispersities) Step-growth polym. Process in solution PU, 43,50,74,92,104,[148][149][150][151][152][153][154][155][156][157][158][159][160] PES, 43,70,148 PA 148 Bifunctional mechanophore used as monomer (functionalization with OH, NCO or COOH) Multiple mechanosensitive units throughout the backbone Versatile method Coupling Synthesis of a functional polymers (generally using controlled/living polym.) PEG, 162 PMA, 104 PS, 98,102,164 copolymers, 58,163,165 metal-NHC polymers complexes: PTHF; 89,113,115,161,166 PS; 89,113,115,161,166 PIB 89,113,115,161,166 Post-polymerization coupling steps (amidification, oxidation, Diels-Alder reaction, etc.. .…”

“…Prior to the stepgrowth polymerization process, the mechanophore needs to be functionalized with one of the reactive functions involved in the polymerization. 43,50,74,92,[148][149][150][151][152][153][154][155][156][157][158][159][160] Using this strategy, Lee et al 154 described the first incorporation of SP in a PU by functionalizing the mechanophore with isocyanate moieties through the reaction of dihydroxyspiropyran with an excess of methylene diphenyldiisocyanate. The subsequent stoichiometric reaction with an hydroxyl-terminated poly(tetramethylene glycol) and a chainextender (Fig.…”

Enhancement of Sensitivity for Retroreflection‐Based Biosensor by Controlling Polymer Brush on Janus Particles

“…Preparation of SP-Siloxy-Terminated PGT via the GT Method: PET was first synthesized as previously described; [47,[54][55][56][57] MC (270 g), 1,4butanediol (18.55 mL), and BF3•THF (1.746 mL) were added to the reaction vessel under anhydrous conditions at 25 °C. After thoroughly mixing, 118 g of ECH and 92 g of THF 92 g were transferred to a dropping funnel.…”