Liquid‐phase catalytic thermal cleavage of thiocarbonylthio end‐groups for polymers synthesized by RAFT polymerization: Influences of different solvents

Catalytic thermal cleavage of thiocarbonylthio end‐groups for RAFT synthesized polymers is usually accompanied by other side reactions such as chain‐scission and crosslinking. Occurrence of these side reactions depends on polymers, end‐groups, and oxidation–reduction property of reaction media in a liquid phase. Herein, well‐defined hydrophilic poly(4‐vinylpridine) (P4VP) and hydrophobic polystyrene (PS) are synthesized via a controlled RAFT polymerization in the presence of S‐1‐Dodecyl‐S′‐(R,R′‐dimethyl‐R″‐acetic acid) trithiocarbonates (DDMAT). Then their thiocarbonylthio end‐groups are cleaved through catalytic thermolysis in a liquid phase. Under the catalysis of Cu(0), all S‐containing groups can be removed at 165 °C in 3 h. To study the effect of solvent on thermolysis and microstructure of polymer, nitrobenzene of oxidation property and diethylene glycol of reduction property are chosen as solvents. Because of oxidizing property of nitrobenzene, Z groups of RAFT agent are eliminated at the same time that thiocarbonylthio end‐groups are removed. Therefore crosslinking among multipolymer chains occurs. While diethylene glycol is used as a solvent, no crosslinking occurs. Diethylene glycol is superior to nitrobenzene for synthesis of well‐defined polymer without S‐containing groups. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43992.