Macromolecular design and application using Mn₂(CO)₁₀‐based visible light photoinitiating systems

Abstract

The environmentally friendly Mn 2 (CO) 10 -based visible light photoinitiating system is a powerful method for the preparation of linear and crosslinked polymeric structures. From a practical point of view, the most important feature of this initiating system is its optical characteristics in the visible range with high quantum yield and good solubility properties. This photoinitiating system is applicable for a variety of monomers that can be polymerized via either radical or cationic mechanisms. Various complex macromolecular structures such as telechelic polymers, block and graft copolymers, polymer networks and surface modifications can be simply prepared by using halogenated precursors. This photoinitiating system is also combined with controlled radical polymerization techniques providing a mild and efficient method for polymer synthesis.

Living Cationic Polymerization of Vinyl Ethers through a Photoinduced Radical Oxidation/Addition/Deactivation Sequence

“…The promising field of photoiniated controlled polymerization is further extended by the ring-opening metathesis polymerization reported by Boydston et al [17] Although photoinitiated cationic polymerization has been known and industrially applied for decades, [18] possibilities to develop new variations to adapt this process to CLP have scarcely been investigated. [23] In the authors laboratory, a broad range of complex macromolecular structures, including block [24] and graft copolymers, [25] and hyper-branched polymers [26] have been prepared either through photoinduced radical and cationic polymerizations. [19] In a recent study, metal-free, visible-light-initiated, living cationic polymerization of p-methoxystyrene was achieved by regulating the cationic chain end in a manner similar to the RAFT process.…”

“…Most of these approaches are based on photoinduced electron-transfer reactions. [23] In the authors laboratory, a broad range of complex macromolecular structures, including block [24] and graft copolymers, [25] and hyper-branched polymers [26] have been prepared either through photoinduced radical and cationic polymerizations. A similar photoinduced redox strategy has been applied to azide-alkyne click reactions, which also utilize Cu I species.…”

“…[14] It was recently demonstrated that the photoinduced ATRP method can also be applied in completely organic systems by using phenothiazines [15] and dyes [16] as photoreductants. [23] In the authors laboratory, a broad range of complex macromolecular structures, including block [24] and graft copolymers, [25] and hyper-branched polymers [26] have been prepared either through photoinduced radical and cationic polymerizations. The promising field of photoiniated controlled polymerization is further extended by the ring-opening metathesis polymerization reported by Boydston et al [17] Although photoinitiated cationic polymerization has been known and industrially applied for decades, [18] possibilities to develop new variations to adapt this process to CLP have scarcely been investigated.…”

Synthesis of Polysulfone Based Amphiphilic Graft Copolymers by a ‘Grafting to’ Approach

“…Based on these fundamental advantages, these systems have been the basis of some interesting fields (three-dimensional object construction, dental fillings, etc.) 32 In the current study, we report a "grafting from" procedure for the synthesis of PSU-based graft copolymers via Mn 2 (CO) 10 photochemistry. 23 Large number of photoinitiators with different absorption characteristics have been developed and used for these applications.…”

Photoinitiated Metal Free Living Radical and Cationic Polymerizations

“…Combining photoinduced electron transfer reactions developed for the conventional systems with controlled polymerization techniques has recently revolutionized the synthesis of well-defined macromolecular architectures [6]. Many attempts have been devoted to apply photochemical systems to existing controlled/living polymerization methodologies by photochemically effecting initiation, mediation and control of these processes [7][8][9][10][11][12][13][14][15][16][17][18][19].…”