Reversible addition-fragmentation transfer RAFT radical polymerization

The fifty chapters submitted for publication in the ACS Symposium series could not fit into one volume and therefore we decided to split them into two volumes. In order to balance the size of each volume we did not divide the chapters into volumes related to mechanisms and materials but rather to those related to atom transfer radical polymerization (ATRP) and to other controlled/living radical polymerization methods reversible-addition fragmentation transfer (RAFT) and other degenerative transfer techniques, as well as stable free radical pol5mierizations (SFRP) including nitroxide mediated polymerization (NMP) and organometallic mediated radical polymerization (OMRP). 

Controlled Radical Polymerization (CRP) is the most recently developed polymerization technology for the preparation of well defined functional materials. Three recently developed CRP processes are based upon forming a dynamic equilibrium between active and dormant species that provides a slower more controlled chain growth than conventional radical polymerization. Nitroxide Mediated Polymerization (NMP), Atom Transfer Radical Polymerization (ATRP) and Reversible Addition Fragmentation Transfer (RAFT) have been developed, and improved, over the past two decades, to provide control over radical polymerization processes. This chapter discusses the patents issued on ATRP initiation procedures, new functional materials prepared by CRP, and discusses recent improvements in all three CRP processes. However the ultimate measure of success for any CRP system is the preparation of conunercially viable products using acceptable economical manufacturing procedures. 

There are several techniques for performing CRP, but the most popular and successful ones so far are as follows stable free radical (SFR) or nitroxide-mediated radical polymerization (NMRP) [44, 45, 49], atom transfer radical polymerization (ATRP) [50, 51], and degenerative transfer techniques, including particularly reversible addition-fragmentation transfer (RAFT) polymerization [3]. These are examined in some detail in the following sections. 

Controlled/ living radical polymerization (CLRP) processes are well-established synthetic routes for the production of well-defined, low-molecular weight-dispersity polymers [99]. The types of CLRP processes (initiator-transfer agent-terminator (INIFERTER), atom transfer radical polymerization (ATRP), nitroxide-mediated radical (NMRP) polymerization, reversible addition-fragmentation transfer (RAFT)) and their characteristics are described in Section 3.8 of Chapter 3 and in Section 14.8 of Chapter 14. 

It is of obvious interest to explore the use of other polymerization techniques that, being more tolerant to the experimental conditions and monomers, can produce amphiphilie azobenzene BCPs with no need for post reactions. Notably, Su et al. have reeently reported the synthesis of such an amphiphilic diblock copolymer with PAA as the hydrophilic block using reversible addition-fragmentation transfer (RAFT) polymerization (structure d in Fig. 6.2) (Su et al., 2007). Using RAFT, they prepared PAA capped with dithiobenzoate and used it as the macro-RAFT transfer agent to polymerize the hydrophobic azobenzene polymer successfully. It ean be expected that more amphiphilic azobenzene BCPs will be synthesized using the eontrolled radical polymerization techniques (ATRP and RAFT) because of their simplicity, versatility, and efficiency. 

Heterogeneous controlled radical polymerization Reversible addition fragmentation transfer (RAFT) process... 

Molecularly imprinted polymers (MIPs) that are capable of sensing specific organophosphorus compounds, such as pinacolyl methylphosphonate (PMP), by luminescence have been synthesized and characterized. The polymers have been synthesized using conventional free radical polymerization and using Reversible Addition Fragmentation Transfer (RAFT) polymerization. The RAFT polymers exhibited many advantages over conventional free radical processes but are more difficult to make porous. 

Currently three systems seem to be the most efficient processes for conducting a CRP nitroxide mediated polymerization (NMP) (eq. 1 in Fig. 5), atom transfer radical polymerization (ATRP) (eq. 2 in Fig. 5) and degenerative transfer systems (eq. 3 in Fig. 5) such as reversible addition-fragmentation transfer (RAFT) or iodine degenerative transfer (IDT) processes (88-90). The key feature of all CRPs is the dynamic equilibration between active radicals and various types of dormant species. 

Three basic concepts concerning stable free-radical polymerization (SFRP) also called nitroxide-mediated radical polymerization (NMP), atom-transfer radical polymerization (ATRP) and reversible addition-fragmentation transfer (RAFT) have been developed during the last decade. 

Phosphoranyl radicals can be involved [77] in RAFT processes [78] (reversible addition fragmentation transfer) used to control free radical polymerizations [79]. We have shown [77] that tetrathiophosphoric acid esters are able to afford controlled/living polymerizations when they are used as RAFT agents. This result can be explained by addition of polymer radicals to the P=S bond followed by the selective p-fragmentation of the ensuing phosphoranyl radicals to release the polymer chain and to regenerate the RAFT agent (Scheme 41). 

Representative structm-e is Si/Si02//tethered block-6-outer block ATRP—atom transfer radical polymerization, RATRP—reverse atom transfer radical polymerization, RAFT—reversible addition fragmentation transfer polymerization... 

Reversible addition-fragmentation transfer polymerization (RAFT) typically utilizes a dithioester transfer agent to control the concentration of propagating radicals (equation 97). ... 

Reversible addition-fragmentation chain transfer (RAFT) radical polymerization... 

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