Dithiocarbamates in RAFT Polymerization

RAFT-Based Polymers for Click Reactions

“…RAFT-based polymers are a versatile source of macromolecules with chain-end thiols, which are suitable for various thiol–X click reactions (X = -ene, -yne, Hal, etc.) and for further modification of chain-end functionality ( Scheme 13 ) [ 41 , 42 , 43 , 44 , 45 , 46 , 47 ].…”

“…The thermolysis of RAFT-based polymers helps to remove the ZC(=S) group and produce polymers with the C=C end group (except xanthates, see 3.1) [ 41 , 42 , 43 , 44 , 45 , 46 , 47 ]. Thermal stability of RAFT-based polymers, mechanism of thermolysis, and purity of the product depend on the nature of the terminal monomer unit and thiocarbonylthio species [ 165 , 166 , 167 , 168 , 169 , 170 , 171 , 172 , 173 , 174 , 175 , 176 , 177 , 178 ].…”

“…To meet this condition, one needs to use a RAFT agent that is effective in the polymerization of chosen monomers, to avoid side reactions (such as intermediate radical termination), and to choose an appropriate ratio of the RAFT agent to initiator ([RAFT agent]/[initiator] >> 1). Nowadays, hundreds of RAFT agents with various types of R and Z groups have been described and applied to the controlled synthesis of (co)polymers [ 41 , 42 , 43 , 44 ]. Besides, the approaches for quantitative modification of the thiocarbonylthio group, resulting in its conversion into –SH, –CH=CXY, –CH 2 –CHXY, –R′ (product of the free radical initiator decomposition), –O–NR 1 R 2 , etc., have been developed [ 45 , 46 , 47 ].…”