Use of Fluorinated Organic Compounds in Living Radical Polymerizations

Abstract

Controlled/living radical polymerization (LRP) is a field of special interest because it allows tailoring well-defined macromolecular architectures such as telechelic, block, graft or star copolymers. Since the eighties, several techniques have been reported [such as the iniferter method, nitroxide-mediated radical polymerization (NMP), atom transfer radical polymerization (ATRP), iodine transfer polymerization (ITP), and reversible addition-fragmentation chain transfer (RAFT)] giving rise to a huge number of publications and patents. This review aims at illustrating the contribution of fluorinated organic compounds in this area of research through the use of fluorinated initiators (dithiocarbamates, xanthates, tetraphenylethanes, alkoxyamines, fluorinated alkyl halides, and dithioesters) or other fluorinated molecules (ligands, solvents). Another point depicts the LRP of various fluorinated monomers (methacrylates, acrylates, styrenics, and alkenes). Finally, fluorinated block and graft copolymers prepared by LRP have been reported. A review with 165 references.

Controlled Radical Ab Initio Emulsion Polymerization of n‐Butyl Acrylate by Reverse Iodine Transfer Polymerization (RITP): Effect of the Hydrolytic Disproportionation of Iodine

“…As the effective amount of iodine n I2,effective involved in the RITP mechanism is lower than the theoretical one n I2,initial (a ¼ n I2,effective /n I2,initial ), the experimental molecular weight is higher than expected [Equation (2)]. M n;targeted ðcorrectedÞ ¼ ðmass of monomerÞ=ð2a  n I2;initial Þ þ M AÀI (2) If taking into account the disproportionation of iodine I 2 [Equation (2)], one would expect a theoretical molecular weight of 15.22/(2  0.33  7.5  10 À4 ) þ 253 ¼ 31 000 g Á mol À1 at 100% conversion. At 99% conversion, an experimental molecular weight of 31 000 g Á mol À1 was observed.…”

“…[1,2] Among CRP, the most widespread methods are nitroxide-mediated polymerization (NMP), [3] atom transfer radical polymerization (ATRP), [4] iodine transfer polymerization (ITP), [5,6] and reversible addition-fragmentation chain transfer polymerization (RAFT/ MADIX). [7] All these methods rely on a reversible activation-deactivation of the growing polymer chains.…”

Cobalt(II) octanoate and cobalt(II) perfluorooctanoate catalyzed atom transfer radical polymerization of styrene in toluene and fluorous media—A versatile route to catalyst recycling and oligomer formation

“…This concept was developed by Horvath and Rabai62, 63 as a very versatile synthetic method in organic synthesis involving small molecules 64–66. But recently, the use of fluorinated organic compounds in living radical polymerization has become popular as well 67. For example, De Campo used CuCl/Pentakis‐ N ‐(4,4,5,5,6,6,7,7,8,8,9,9,10,10,11,11,11‐heptadecafluoroundecyl)‐1,4,7‐triazaheptane for atom transfer radical addition reactions and cyclizations to obtain products with low copper contamination 68…”

Migration of Additives in Polymer Coatings: Phosphonated Additives and Poly(vinylidene chloride)‐Based Matrix

“…A convenient method to control both the molecular weight and the architecture of polymers is controlled/living radical polymerization (CRP). [19,20] The aim of this study is to investigate the migration of an additive in a matrix by scanning electron microscopy (SEM). For this purpose, several polymers were synthesized: one of high molecular weight to play the role of the matrix, and others of lower molecular weights but of similar composition to act as additives.…”