Chain transfer by radical addition-fragmentation mechanisms: Synthesis of macromonomers and end-functional oligomers

Appropriately substituted allylic sulfides, sulfones, bromides, phosphonates, stannanes and peroxides, vinyl ethers and thionocarbonyl compounds are effective chain transfer agents in free radical polymerizations. These compounds function by a radical addition-fragmentation mechanism by which fragments derived from the chain transfer agents are installed at both ends of polymer chains. This provides a convenient method for preparing both mono- and di-end functional oligomers and polymers. Allylic peroxides fragment to give epoxy end groups while the other allylic compounds give rise to macromonomers by introducing terminal double bonds.