Atom-Transfer Radical Polymerization of a SuFExable Vinyl Monomer and Polymer Library Construction via SuFEx Click Reaction

Abstract

The advancement in the synthesis of functional polymeric materials has greatly benefited from the development of functionalized monomers and effective polymerization methods. Here, inspired by the controlled radical polymerization and the new generation of click chemistry, sulfur­(VI) fluoride exchange (SuFEx), we introduce a SuFExable vinyl monomer, 4-vinylbenzenesulfonyl fluoride (VBSF), which shows a good balance of stability and reactivity and can readily undergo organocatalytic atom-transfer radical polymerization under visible light with good controls and high end-group fidelity, while retaining the sulfonyl fluoride groups intact. Moreover, poly­(VBSF) can be further modified with high efficiency via SuFEx reactions with various aryl silyl ethers, thus allowing a rapid construction of a functional polymer library in a click fashion.

A guide to functionalisation and bioconjugation strategies to surface-initiated polymer brushes

“…126 Several click reactions have been reported for the functionalization of polymer brushes, among them cycloadditions, such as Diels-Alder and alkyne-azide reactions, and thiol-ene couplings, including Michael additions and radical thiolalkene and thiol-alkyne reactions remain the most widely applied. 103,104,127,128 However, other emerging highly efficient reactions, such as sulfur(VI) fluoride exchange chemistry (SuFEx) [129][130][131] and hetero-disulfide exchange reactions 120,132,133 have received some attention for side-chain and end-chain functionalisation of brushes. Associated with this diversity, some of the members of click chemistries are orthogonal (e.g.…”

Design and Synthesis of a New Indazole-Decorated RAFT Agent for Highly Efficient PET-RAFT Polymerization

“…Photocontrolled reversible deactivation radical polymerization (photo-RDRP) makes use of light energy to control production of polymers with precise molecular weight, composition, and architecture under ambient conditions. − Unlike cationic and anionic polymerization, − photo-RDRP is compatible with diverse solvents, including aqueous solutions. − A good example of such systems is photoinduced electron/energy transfer reversible addition–fragmentation chain transfer (PET-RAFT) polymerization catalyzed by zinc tetraphenyl porphyrin (ZnTPP), a sustainable and biocompatible photocatalyst (PC). − Notably, ZnTPP-catalyzed PET-RAFT systems are capable of controlling oxygen-present radical polymerization, because its populated triplet excited states ( 3 PC*) can transform ground-state oxygen (O 2 ) into singlet oxygen ( 1 O 2 ), allowing for subsequent elimination by vinyl monomers or the solvent . They are even compatible to open-air conditions, potentially suitable for a broad spectrum of aerobically biological and photocuring applications. − …”

Harnessing the photo-acidity of organic dyes for the development of ring-opening polymerization of lactones under visible light

“…Visible light-regulated polymerizations provide a powerful approach for the synthesis of well-defined polymers, with a simultaneous, non-invasive control by low energy light in spatial and temporal dimensions. 1,2 In the past decade, considerable efforts have been devoted to the development of visible light-mediated polymerization methods, and significant advancement has been achieved in photocontrolled radical polymerization, [3][4][5][6][7][8][9][10][11][12][13][14][15][16][17] cationic polymerization, [18][19][20][21][22][23] photo-redox ring-opening metathesis polymerization, [24][25][26][27][28] etc. In contrast, photocontrolled ring-opening polymerization (ROP) of lactones is a relatively underdeveloped field, and scarcely mediated by environmentally benign visible light.…”