Combination of AGET ATRP and SuFEx for post-polymerization chain-end modifications

Abstract

a b s t r a c tPost-polymerization modification of polymer chain-ends is a powerful tool for the preparation of functional materials. "Click" type reactions represent the most prevalent post-polymerization strategies. We applied the recently described sulfur(VI) fluoride exchange reaction to functionalize the chain-ends of four polymers prepared using activators generated by electron transfer atom transfer radical polymerization. Aryl-TBDMS terminated polymers were reacted with aryl sulfurofluoridate compounds with a near quantitative conversion. This research represents the application of a new click type reaction to prepare functional polymers.

Bifluoride-catalysed sulfur(VI) fluoride exchange reaction for the synthesis of polysulfates and polysulfonates

“…With these catalysts, the reaction between aryl fluorosulfates (or aryl sulfonyl fluorides) and aryl silyl ethers exclusively affords diaryl sulfates (or diaryl sulfonates). The SuFEx reaction has been successfully applied to the synthesis of aromatic polysulfates and polysulfonates by our group 7,8 , and to post-polymerization modifications by others 9–11 .…”

SuFEx‐Based Polysulfonate Formation from Ethenesulfonyl Fluoride–Amine Adducts

“…[10] Since then, SuFEx has been successfully applied to surface modification, polymer synthesis, and post-polymerization modification. [11] We discovered that 1,8-diazabicycloundec-7-ene (DBU) and 2- tert -butylimino-2-diethylamino-1,3-dimethylperhydro-1,3,2-diazaphosphorine (BEMP) could initiate the SuFEx-based polycondensation reaction of bisphenol A bis( t -butyldimethylsilyl) ethers and bisphenol A bis(fluorosulfate) to form polysulfates with high number-average molecular weight ( M n ), narrow polydispersity, and near quantitative yields. Compared to bisphenol A-derived polycarbonate, which is a widely used thermoplastic polymer, the bisphenol A-based polysulfates exhibit better thermal and hydrolytic stability, implicating potential applications under harsh environments.…”

“…[12-13] The poor selectivity of sulfonyl chlorides in this process significantly limits the utility of these methods, and as a consequence, the structures of currently available polysulfonates are quite limited. [10, 11c] …”

“…On the other hand, the synthesis of bisphenol bis( t -butyldimethylsilyl) ethers (BB monomers) is accomplished by reacting t -butyldimethylsilyl chloride with bisphenols. [11c] .…”

Crystal structure of methyl 1-(2-(fluorosulfonyl)ethyl)-2-oxocyclopentanecarboxylate, C9H13FO5S

“…Sulfonyl fluorides (SF) are considered as a versatile functional group owing to its widespread applications [6][7][8][9][10]. The moiety has sparked interest in drug discovery, as it has shown to be an inhibitor for numerous proteins [11,12].…”