Highly functionalized thermoplastic polyurethane from surface click reactions

Abstract

Thermoplastic polyurethane (TPU) functionalized with azido groups is useful because not only it allows the convenient introduction of various desired functional groups via the azide-alkyne click reaction, but also it is elastic, flexible, and easily proccessable. However, after undergoing click reaction with useful functional groups on polymer chain directly, the polymer becomes hard and non-soluble in organic solvents, losing its useful properties. Therefore, a surface click reaction is performed on the azido TPU electrospun fiber to introduce specific functional groups (here amine and guanidine for catalytic reaction). The amine-and guanidine-treated TPU fibers effectively convert diisopropyl fluorophosphates-the simulant of toxic nerve gases-and 2,2-dichlorovinyl dimethyl phosphate-one of the insecticides to a non-toxic product via decontamination by hydrolysis, with the amine and guanidine functional groups acting as nucleophilic catalysts.Here, we synthesized easily proccessable azido TPU and introduced useful functional groups via a click reaction. Organobasic moieties were introduced onto pre-structured azido TPU (i.e., the nanofiber web from electrospinning) via a surface click reaction with quite high yield. The resulting nanofiber web with tailored functional groups could be used as a catalytic membrane for the detoxification of toxic chemicals, including chemical warfare agents (CWAs) and insecticides. 17 EXPERIMENTAL MaterialsTo synthesize azido TPU, methylene chloride (MC) (99.5%), tetrahydrofuran (THF) (99.5%), N,N 0 -dimethylformamide (DMF) Additional Supporting Information may be found in the online version of this article.

Mass‐Production of Electrospun Carbon Nanofiber Containing SiOx for Lithium‐Ion Batteries with Enhanced Capacity

“…Additionally, the HPRC system provides nanofibers with a highly rapid production rate (0.5 g h −1 for a lab‐scale) (Figure d). Given that conventional single‐needle electrospinning uses 5–10 wt% polymeric solutions and its feed rate ranges from 0.1 to 1.0 mL h −1 , a theoretically obtainable amount of nanofiber exhibited a maximum at the rate of 0.1 g h −1 . In our experiment, we obtained the nanofiber by using single needle‐based electrospinning system relative to a rate of 0.097 g h −1 .…”

Detoxification Properties of Guanidinylated Chitosan Against Chemical Warfare Agents and Its Application to Military Protective Clothing

“…Choi et al discussed the guanidine group treatment of a thermoplastic polyurethane fiber for nerve agent decontamination. The guanidine-treated thermoplastic polyurethane showed only 50% DFP hydrolysis to DHP in 2 h at 32 °C [ 10 ]. In addition, Chen et al reported on the functionalization of PAN fibers by hydroxylamine hydrochloride for nerve agent decontamination.…”

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

“…Although easy processibility and large amount of functional groups in chain will be the best advantages of polymers, simultaneous achievement of both properties are really challenging 25 . For example, as increasing amount of functional moiety (with desired molecules i.e organic dyes), the solvent property of polymers will be changed, and thus re-optimization of processing should be followed.…”