Open-to-Air RAFT Polymerization on a Surface under Ambient Conditions

Abstract

Oxygen (O2)-mediated controlled radical polymerization was performed on surfaces under ambient conditions, enabling on-surface polymer brush growth under open-to-air conditions at room temperature in the absence of metal components. Polymerization of zwitterionic monomers using this O2-mediated surface-initiated reversible addition fragmentation chain-transfer (O2-SI-RAFT) method yielded hydrophilic surfaces that exhibited anti-biofouling effects. O2-SI-RAFT polymerization can be performed on large surfaces under open-to-air conditions. Various monomers including (meth)­acrylates and acrylamides were employed for O2-SI-RAFT polymerization; the method is thus versatile in terms of the polymers used for coating and functionalization. A wide range of hydrophilic and hydrophobic monomers can be employed. In addition, the end-group functionality of the polymer grown by O2-SI-RAFT polymerization allowed chain extension to form block copolymer brushes on a surface.

Formation of Various Polymeric Films via Surface‐Initiated ARGET ATRP on Silicon Substrates

“…OEGMA, DMAEMA, SPMA, and MPDSAH were used as monomers for SI‐ARGET ATRP in this study. A zwitterionic monomer, MPDSAH was synthesized as described in the previously published literature 24 . Prior to SI‐ARGET ATRP, monomers except MPDSAH and SPMA were purified through column chromatography (basic Al 2 O 3 ) to remove a polymerization inhibitor.…”

Oxygen Tolerance in Surface-Initiated Reversible Deactivation Radical Polymerizations: Are Polymer Brushes Turning into Technology?

“…50,51 In this system, a cyclic process occurs: R 3 B reacts with oxygen molecules to form alkyl radicals that react with oxygen to form peroxyl radicals that react again with R 3 B, forming alkyl radicals. 50 Through this process, both oxygen quenching and polymerization initiation by radical formation are facilitated by R 3 B at room temperature in the presence of air. This chemistry has been employed for the performance of solution RAFT polymerizations 51,52 and has been extended to surfaces, establishing what is known as oxygen-mediated surface-initiated RAFT (O 2 -SI-RAFT) to form polymer brush surface coatings.…”

Cell-membrane-inspired polymers for constructing biointerfaces with efficient molecular recognition

“…224,225 Representative living radical polymerization procedures, such as reversible additionfragmentation chain-transfer (RAFT) polymerization and atom transfer radical polymerization (ATRP) (SI-ATRP), have been examined to prepare well-defined polymer brush layers on substrates. [226][227][228][229][230][231] Precise control of the MW and density of the polymer chains on the surface can be achieved. Moreover, the addition of a different monomer after polymerization of a specific monomer causes further polymer-chain elongation reactions, facilitating synthesis of block-type polymers.…”