Hydroperoxide Traces in Common Cyclic Ethers as Initiators for Controlled RAFT Polymerizations

Area of Science:

• Polymer Chemistry
• Materials Science

Background:

• Conventional radical polymerization often requires specific initiators.
• Hydroperoxide contaminants in solvents can initiate unwanted radical reactions.
• Controlled polymerization techniques like RAFT are crucial for tailored polymer properties.

Purpose of the Study:

• To develop an initiator-free RAFT polymerization method.
• To utilize common solvent contaminants as radical sources.
• To demonstrate controlled synthesis of polymers with high livingness.

Main Methods:

• Employed reversible addition-fragmentation chain transfer (RAFT) polymerization.
• Utilized hydroperoxide-contaminated cyclic ether solvents (e.g., THF, dioxane) as radical sources.
• Polymerized reactive monomers such as N-acryloylpyrrolidine and N,N-dimethylacrylamide.

Main Results:

• Achieved well-controlled polymerizations without conventional radical initiators.
• Demonstrated the living nature of the polymers, enabling block copolymer synthesis.
• Successfully synthesized tailored polymers using minimal experimental effort.

Conclusions:

• Solvent-initiated RAFT polymerization is a viable and straightforward method for polymer synthesis.
• This approach simplifies material preparation using standard laboratory equipment.
• The coinitiating ability of solvents must be considered for precise kinetic studies and high-livingness polymer synthesis.