SuFEx on the Surface: A Flexible Platform for Postpolymerization Modification of Polymer Brushes

Area of Science:

• Polymer Chemistry
• Surface Science
• Organic Synthesis

Background:

• Polymer brushes offer tunable surface properties but are limited by monomer compatibility during growth.
• Post-polymerization modification using click chemistry is effective but struggles with unprotected moieties.
• Existing methods face challenges in incorporating diverse functionalities directly onto polymer brushes.

Purpose of the Study:

• To introduce a new click chemistry method, sulfur(VI) fluoride exchange (SuFEx), for polymer brush modification.
• To demonstrate the efficiency and versatility of SuFEx for functionalizing polymer brushes.
• To overcome limitations of traditional polymerization and modification techniques.

Main Methods:

• Grew polymer brushes via free-radical polymerization incorporating native -SO2F groups.
• Applied SuFEx click chemistry to quantitatively attach silyl ethers to the polymer brushes.
• Utilized SuFEx for post-polymerization modification with alkynes, thiols, and dienes.

Main Results:

• Achieved rapid, quantitative click reactions with pseudo-first-order rates up to 0.04 s⁻¹.
• Successfully demonstrated the facile introduction of silyl ethers onto polymer brushes.
• Showcased the orthogonal reactivity of SuFEx for adding diverse functional groups like alkynes, thiols, and dienes.

Conclusions:

• SuFEx click chemistry provides an efficient and versatile platform for polymer brush functionalization.
• This method overcomes limitations of monomer compatibility and post-polymerization modification challenges.
• SuFEx enables the facile creation of advanced polymer brush architectures with tailored surface functionalities.