High-Throughput Tertiary Amine Deoxygenated Photopolymerizations for Synthesizing Polymer Libraries

Area of Science:

• Polymer Chemistry
• Materials Science
• Chemical Engineering

Background:

• Traditional radical polymerizations require deoxygenation, limiting throughput.
• Exploring vast polymer chemical space is crucial for discovering new materials.
• Photopolymerization offers potential for faster, in-air synthesis.

Purpose of the Study:

• Develop a high-throughput protocol for synthesizing polymer libraries.
• Enable rapid exploration of polymer chemical space.
• Facilitate the discovery of novel polymer formulations.

Main Methods:

• Utilized liquid handling robots and multichannel pipettes for automated synthesis.
• Employed blue light photolysis of reversible addition fragmentation chain transfer agents.
• Integrated tertiary amine deoxygenation for in-air polymerization in 96-well plates.
• Investigated solvent effects, optimizing for hydrophobic monomer copolymerization using dioxane.

Main Results:

• Successfully synthesized 392 polymers in under 40 hours.
• Achieved in-plate isolation of pure polymers using dioxane and in-plate evaporation or precipitation.
• Demonstrated reproducibility through 96-well plate size exclusion chromatography analysis.
• Identified limitations in molecular weight and dispersity control with dioxane compared to DMSO, particularly for acrylates.

Conclusions:

• The developed protocol enables rapid, large-scale synthesis of polymer libraries.
• This method facilitates efficient exploration of chemical space for materials discovery.
• The system provides a format amenable to high-throughput screening and identification of promising polymer candidates.