Surface-Initiated Living Radical Polymerizations Using Iodine, Organotellurium, and Organic Catalysts

Goto, Atsushi; Tsujii, Yoshinobu

doi:10.1007/12_2015_310

Cited by 2 publications

(1 citation statement)

References 67 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…The surface of a material plays crucial roles in many important properties such as thermodynamic, mechanical, chemical, and biological properties as an interface to external phases. − Surface-initiated graft polymerization, in which polymerization is conducted from an initiator bound to a surface, is among the most effective surface modification methods. The use of LRP in surface-initiated graft polymerization can afford a polymer brush with a high surface density.…”

Section: Resultsmentioning

confidence: 99%

Solvent-Selective Reactions of Alkyl Iodide with Sodium Azide for Radical Generation and Azide Substitution and Their Application to One-Pot Synthesis of Chain-End-Functionalized Polymers

Wang

Goto

2017

J. Am. Chem. Soc.

Self Cite

View full text Add to dashboard Cite

Herein, a new reaction of an alkyl iodide (R-I) with an azide anion (N) to reversibly generate the corresponding alkyl radical (R) is reported. Via this new reaction, N was used as an efficient catalyst in living radical polymerization, yielding a well-defined polymer-iodide. A particularly interesting finding was the solvent selectivity of this reaction; namely, R-I and N generated R in nonpolar solvents, while the substitution product R-N was generated in polar solvents. Exploiting this unique solvent selectivity, a one-pot synthesis of polymer-N was attained. N was first used as a catalyst for living radical polymerization in a nonpolar solvent to produce a polymer-iodide and was subsequently used as a substitution agent in a polar solvent by simply adding the polar solvent, thereby transforming the polymer-iodide to polymer-N in one pot. This one-pot synthesis was further applied to obtain N-chain-end-functionalized polymer brushes on the surface, uniquely controlling the N coverage (number density). Using the chain-end N, the obtained linear and brush polymers were connected to functional molecules via an azide-alkyne click reaction. The attractive features of this system include facile operation, access to unique polymer designs, and no requirement for using excess NaN. In addition to N, thiocyanate (SCN) and cyanate (OCN) anions were also studied.

show abstract