Activation and Deactivation of Chain-transfer Agent in Controlled Radical Polymerization by Oxygen Initiation and Regulation

New method for controlled synthesis of polylactide block copolymers: organoborane/p‐quinone system and reversible‐deactivation radical polymerization

“…There has been an increased interest in polymer synthesis using boron-containing compounds. [22][23][24][25][26][27][28][29][30][31][32][33][34] One of the benefits of polymerization in the presence of organoboranes is a high rate of initiation at ambient temperature even in the presence of atmospheric oxygen. Chung et al discovered that polymerization of some monomers in the presence of a trialkylborane/atmospheric oxygen system proceeds in a controlled manner due to the dissociation-recombination of active terminal borane fragments.…”

“…47 Further, Pan and co-workers developed a method for carrying out RAFT polymerization using the triethylborane/ atmospheric oxygen system as an initiator. [27][28][29][30][31] This method has many prospects in terms of obtaining various polymeric materials with well-defined structure, endowed with a range of unique properties. An original synthetic route for the production of multiblock copolymers based on lactide, epoxides, anhydrides and vinyl monomers in the presence of triethylborane was provided by Wang and co-workers.…”

“…An interesting way to realize RDRP is the use of organoborane‐based systems that serve as initiators as well as regulators of polymerization. There has been an increased interest in polymer synthesis using boron‐containing compounds 22–34 . One of the benefits of polymerization in the presence of organoboranes is a high rate of initiation at ambient temperature even in the presence of atmospheric oxygen.…”

“…For example, they are used as initiators for producing polymeric bone cement 47 . Further, Pan and co‐workers developed a method for carrying out RAFT polymerization using the triethylborane/atmospheric oxygen system as an initiator 27–31 . This method has many prospects in terms of obtaining various polymeric materials with well‐defined structure, endowed with a range of unique properties.…”

ATRP of MIDA Boronate-Containing Monomers as a Tool for Synthesizing Linear Phenolic and Functionalized Polymers

“…Nevertheless, one characteristic feature of polymers prepared by RAFT polymerization is the presence of thiocarbonyl end groups, commonly resulting in odor and color, hampering some commercial applications. − In addition, the chain transfer agent (CTA) end group can lead to side reactions and may poison the late transition metal catalysts if the thiol group is formed in the subsequent modification. , In previous work, we observed the undesirable coupling reactions between the CTA end groups of MIDA boronate-containing polymers during the postmodification of Suzuki–Miyaura coupling (SMC) with organohalides. Therefore, the CTA end groups were removed first .…”