Atom transfer radical polymerization (ATRP)

The initiator of the polymerization is usually an organohalogenid and the dormant state is achieved in a metal complex of a transition metal (‘radical buffer’). This method is very versatile but requires unconventional initiator systems that are sometimes poorly compatible with the polymerization media.

Nitroxide-mediated polymerization (NMP)

Given certain conditions a homolytic splitting of the C-O bond in alkoxylamines can occur and a stable 2-centre 3 electron N-O radical can be formed that is able to initiate a polymerization reaction. The preconditions for an alkoxylamine suitable to initiate a polymerization are bulky, sterically obstructive substituents on the secondary amine, and the substituent on the oxygen should be able to form a stable radical, e.g. benzyl.

Example of a reversible deactivation reaction

Reversible addition-fragmentation chain transfer (RAFT)

RAFT is one of the most versatile and convenient techniques in this context. The most common RAFT-processes are carried out in the presence of thiocarbonylthio compounds that act as radical buffers. While in ATRP and NMP reversible deactivation of propagating radical-radical reactions takes place and the dormant structures are a halo-compound in ATRP and the alkoxyamine in NMP, both being a sink for radicals and source at the same time and described by the corresponding equilibria. RAFT on the contrary, is controlled by chain-transfer reactions that are in a deactivation-activation equilibrium. Since no radicals are generated or destroyed an external source of radicals is necessary for initiation and maintenance of the propagation reaction.

Initiation step of a RAFT polymerization

${\displaystyle {\ce {I->I^{.}->[{\ce {M}}]->[{\ce {M}}]P_{\mathit {n}}^{.}}}}$

Reversible chain transfer

Reinitiation step

${\displaystyle {\ce {R^{.}->[{\ce {M}}]RM^{.}->[{\ce {M}}]->[{\ce {M}}]P_{\mathit {m}}^{.}}}}$

Chain equilibration step

Termination step

${\displaystyle {\ce {{P_{\mathit {m}}^{.}}+P_{\mathit {n}}^{.}->P_{\mathit {m}}P_{\mathit {n}}}}}$

Catalytic chain transfer and cobalt mediated radical polymerization

Although not a strictly living form of polymerization catalytic chain transfer polymerization must be mentioned as it figures significantly in the development of later forms of living free radical polymerization. Discovered in the late 1970s in the USSR it was found that cobalt porphyrins were able to reduce the molecular weight during polymerization of methacrylates. Later investigations showed that the cobalt glyoxime complexes were as effective as the porphyrin catalysts and also less oxygen sensitive. Due to their lower oxygen sensitivity these catalysts have been investigated much more thoroughly than the porphyrin catalysts.

The major products of catalytic chain transfer polymerization are vinyl-terminated polymer chains. One of the major drawbacks of the process is that catalytic chain transfer polymerization does not produce macromonomers but instead produces addition fragmentation agents. When a growing polymer chain reacts with the addition fragmentation agent the radical end-group attacks the vinyl bond and forms a bond. However, the resulting product is so hindered that the species undergoes fragmentation, leading eventually to telechelic species.

These addition fragmentation chain transfer agents do form graft copolymers with styrenic and acrylate species however they do so by first forming block copolymers and then incorporating these block copolymers into the main polymer backbone.

While high yields of macromonomers are possible with methacrylate monomers, low yields are obtained when using catalytic chain transfer agents during the polymerization of acrylate and stryenic monomers. This has been seen to be due to the interaction of the radical centre with the catalyst during these polymerization reactions.

The reversible reaction of the cobalt macrocycle with the growing radical is known as cobalt carbon bonding and in some cases leads to living polymerization reactions.

Iniferter polymerization

An iniferter is a chemical compound that simultaneously acts as initiator, transfer agent, and terminator (hence the name ini-fer-ter) in controlled free radical iniferter polymerizations, the most common is the dithiocarbamate type.^[8][9]

Iodine-transfer polymerization (ITP)

Iodine-transfer polymerization (ITP, also called ITRP), developed by Tatemoto and coworkers in the 1970s^[10] gives relatively low polydispersities for fluoroolefin polymers. While it has received relatively little academic attention, this chemistry has served as the basis for several industrial patents and products and may be the most commercially successful form of living free radical polymerization.^[11] It has primarily been used to incorporate iodine cure sites into fluoroelastomers.

The mechanism of ITP involves thermal decomposition of the radical initiator (typically persulfate), generating the initiating radical In•. This radical adds to the monomer M to form the species P₁•, which can propagate to P_m•. By exchange of iodine from the transfer agent R-I to the propagating radical P_m• a new radical R• is formed and P_m• becomes dormant. This species can propagate with monomer M to P_n•. During the polymerization exchange between the different polymer chains and the transfer agent occurs, which is typical for a degenerative transfer process.

Typically, iodine transfer polymerization uses a mono- or diiodo-perfluoroalkane as the initial chain transfer agent. This fluoroalkane may be partially substituted with hydrogen or chlorine. The energy of the iodine-perfluoroalkane bond is low and, in contrast to iodo-hydrocarbon bonds, its polarization small.^[12] Therefore, the iodine is easily abstracted in the presence of free radicals. Upon encountering an iodoperfluoroalkane, a growing poly(fluoroolefin) chain will abstract the iodine and terminate, leaving the now-created perfluoroalkyl radical to add further monomer. But the iodine-terminated poly(fluoroolefin) itself acts as a chain transfer agent. As in RAFT processes, as long as the rate of initiation is kept low, the net result is the formation of a monodisperse molecular weight distribution.

Use of conventional hydrocarbon monomers with iodoperfluoroalkane chain transfer agents has been described.^[13] The resulting molecular weight distributions have not been narrow since the energetics of an iodine-hydrocarbon bond are considerably different from that of an iodine-fluorocarbon bond and abstraction of the iodine from the terminated polymer difficult. The use of hydrocarbon iodides has also been described, but again the resulting molecular weight distributions were not narrow.^[14]

Preparation of block copolymers by iodine-transfer polymerization was also described by Tatemoto and coworkers in the 1970s.^[15]

Although use of living free radical processes in emulsion polymerization has been characterized as difficult,^[16] all examples of iodine-transfer polymerization have involved emulsion polymerization. Extremely high molecular weights have been claimed.^[17]

Listed below are some other less described but to some extent increasingly important living radical polymerization techniques.

Selenium-centered radical-mediated polymerization

Diphenyl diselenide and several benzylic selenides have been explored by Kwon et al. as photoiniferters in polymerization of styrene and methyl methacrylate. Their mechanism of control over polymerization is proposed to be similar to the dithiuram disulfide iniferters. However, their low transfer constants allow them to be used for block copolymer synthesis but give limited control over the molecular weight distribution.^[18]

Telluride-mediated polymerization (TERP)

Telluride-mediated polymerization or TERP first appeared to mainly operate under a reversible chain transfer mechanism by homolytic substitution under thermal initiation. However, in a kinetic study it was found that TERP predominantly proceeds by degenerative transfer rather than 'dissociation combination'.^[19]

Alkyl tellurides of the structure Z-X-R, were Z=methyl and R= a good free radical leaving group, give the better control for a wide range of monomers, phenyl tellurides (Z=phenyl) giving poor control. Polymerization of methyl methacrylates are only controlled by ditellurides. The importance of X to chain transfer increases in the series O<S<Se<Te, makes alkyl tellurides effective in mediating control under thermally initiated conditions and the alkyl selenides and sulfides effective only under photoinitiated polymerization.

Stibine-mediated polymerization

More recently Yamago et al. reported stibine-mediated polymerization, using an organostibine transfer agent with the general structure Z(Z')-Sb-R (where Z= activating group and R= free radical leaving group). A wide range of monomers (styrenics, (meth)acrylics and vinylics) can be controlled, giving narrow molecular weight distributions and predictable molecular weights under thermally initiated conditions.^[20][21] Yamago has also published a patent indicating that bismuth alkyls can also control radical polymerizations via a similar mechanism.

Copper mediated polymerization

More reversible-deactivation radical polymerizations are known to be catalysed by copper.