Carbon-Centered Radical Mediated Polymerization

With the carbon-centered radical-mediated polymerization systems described to date, the propagating radical should be tertiary (e.jg. methacrylate ester) to give reasonable rates of activation. 

The first use of sterically hindered hexasubstituted ethanes [e.g. 33] as initiators of polymerization was reported by Bledzki et The use of related 

su and I azaki have reported on the use of triphenylmethylazobenzene (39) as an initiator. In this case, phenyl radical initiates polymerization and the triphenylmethyl radical reacts mainly by primary radical termination to form a macroinitiator. The early report that triphenylmethyl radical does not initiate MMA polymerization may only indicate a very low rate of polymerization. The addition of triphenylmethyl radical to MMA has been demonstrated in radical trapping experiments.  

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ORl OX w di-Miutyl peroxyoxalalc deactivation by reversible chain transfer and bioinolecular aclivaiion 456 atom transfer radical polymerization 7, 250, 456,457, 458,461.486-98 deactivation by reversible coupling and untmolecular activation 455-6, 457-86 carbon-centered radical-mediated poly nierizaiion 467-70 initiators, inferlers and iriiters 457-8 metal complex-mediated radical polymerization 484... 

Most polymerizations in this section can be categorized as stable (Tree) radical-mediated polymerizations (sometimes abbreviated as SFRMP). In the following discussion systems have been classed according to the type of stable radical involved, which usually correlates with the type of bond homolyzed in the activation process. Those described include systems where the stable radical is a sulfur-ccntered radical (Section 9.3.2), a selenium-centered radical (Section 9.3.3), a carbon-centered radical (Sections 9.3.4 and 9.3.5), an oxygen-centered radical (Sections 9.3.6, 9.3.7), or a nitrogcn-ccntcrcd radical (Section 9.3.8). Wc also consider polymerization mediated by cobalt complexes (Section 9.3.9) and certain monomers (Section 9.3.5). 

The hindered carbon-centered radicals are most suited as mediators in the polymerization of 1,1-disubstituled monomers e.g. MMA,78,95 other methacrylates and MAA,06 and AMS97). Polymerizations of monosubstituted monomers are not thought to be living. Dead end polymerization is observed with S at polymerization temperatures <100°C.98 Monosubstituted monomers may be used in the second stage of AB block copolymer synthesis (formation of the B block).95 However the non-living nature of the polymerization limits the length of the B block that can be formed. Low dispersities are generally not achieved. 

N-Alkoxylamines 88 are a class of initiators in "living" radical polymerization (Scheme 14). A new methodology for their synthesis mediated by (TMSlsSiH has been developed. The method consists of the trapping of alkyl radicals generated in situ by stable nitroxide radicals. To accomplish this simple reaction sequence, an alkyl bromide or iodide 87 was treated with (TMSlsSiH in the presence of thermally generated f-BuO radicals. The reaction is not a radical chain process and stoichiometric quantities of the radical initiator are required. This method allows the generation of a variety of carbon-centered radicals such as primary, secondary, tertiary, benzylic, allylic, and a-carbonyl, which can be trapped with various nitroxides. 

Since the nitroxide and the carbon-centered radical diffuse away from each other, termination by combination or disproportionation of two carbon-centered radicals cannot be excluded. This will lead to the formation of dead polymer chains and an excess of free nitroxide. The build-up of free nitroxide is referred to as the Persistent Radical Effect [207] and slows down the polymerization, since it will favor trapping (radical-radical coupling) over propagation. Besides termination, other side reactions play an important role in nitroxide-mediated CRP. One of the important side reactions is the decomposition of dormant chains [208], yielding polymer chains with an unsaturated end-group and a hydroxyamine, TH (Scheme 3, reaction 6). Another side reaction is thermal self-initiation [209], which is observed in styrene polymerizations at high temperatures. Here two styrene monomers can form a dimer, which, after reaction with another styrene monomer, results in the formation of two radicals (Scheme 3, reaction 7). This additional radical flux can compensate for the loss of radicals due to irreversible termination and allows the poly-... 

The hindered carbon-centered radicals are most suited as mediators in the polymerization of 1,1-disubstituted monomers e.g. other methacrylates... 

In the mid-1980s, the first technique that relies on the reversible termination of radicals with a stable free radical was developed in the group of E. Rizzardo at CSIRO in Australia. Rizzardo and co-workers found that nitroxide-stable free radicals were able to add to carbon-centered radicals to form alkoxy amines (9). In certain cases these alkoxy amines are thermally unstable, so that they enter into an equilibrium between (transient) carbon-centered radical and (persistent) nitroxide radical on one side, and alkoxy amine on the other side. TEMPO was initially the most frequently used nitroxide in conjunction with the polymerization of styrene and its derivatives. The TEMPO-polystyrene adduct requires temperatures of 120° C or above in order to establish an equilibrium at which polymerization takes place. Around the mid-1990s Georges and co-workers focused on the TEMPO-mediated pol5unerization of styrene (10), and developed various strategies to overcome intrinsic weaknesses of the system. They used camphor sulfonic acid to enhance the rate of polymerization (11). This rate enhancement was later elucidated to be due to the destruction of excess nitroxide that builds up during the polymerization. 

Following the large-scale preparation of the vinylicthiolactone monomers 6 and 7, the CRP was targeted. As there were no literature precedents on the compatibility of thiolactone in the presence of carbon-centered propagating radical systems, we adapted polymerization conditions guaranteeing the integrity of the thiolactone moiety. We deliberately avoided the use of metal-mediated CRP in order to completely exclude transition metal residues throughout the processes of monomer synthesis, CRP, and PPM. Hence, RAFT [128-132] and nitroxide-mediated polymerization (NMP) [147] were the preferred polymerization techniques. 

Second, even though the metal center can take two consecutive valence states, some metal centers in a lower valent state may prefer to form a carbon-metal bond upon meeting with the growing radical species rather than activate the more abundant carbon-halogen bond in the dormant termini (Scheme 2-(4)). In this case, if the carbon-metal bonds may be homolytically cleaved with a fast and reversible equilibrium, the polymerization would result in another controlled/living radical polymerization, the so-called organometallic-mediated... 

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