DEPARTAMENTO DE RECURSOS HUMANOS

(RAFT) polymerization

RAFT polymerization has been extensively used to synthesize polymers with narrow molar mass distributions and block copolymers. This technique exhibits good tolerance to a wide range of monomers, solvent and initiators. In addition, it offers control over a wide range of monomers with different classes of chain transfer agent. The mechanism of RAFT polymerization is summarized in Scheme 1.6. The initiation and radical-radical termination occur as in free radical polymerization. Propagating

radicals (Pn•) are formed from the initiator. The addition of Pn• to the thiocarbonylthio

compound (A) followed by fragmentation of intermediate radical (B) results in a

polymeric thiocarbonylthio compound (Aa) and a new radical (R•). Reaction of R•with

monomer forms new propagating radicals (Pm•). A rapid equilibrium between the active

propagating radicals (Pn• and Pm•) and the dormant polymeric thiocarbonylthio

27 production of narrow dispersity polymers. When the polymerization is completed, most of the polymer chains will retain the thiocarbonylthio end group.

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The key of the degenerative chain transfer in RAFT polymerization is the chemical structure of the RAFT agent (Figure 1.3.). The substituents around the C=S are labelled as Z and R and the effectiveness of the RAFT agent depends on the

monomer being polymerized and the transfer constant (Ctr) which is determined by the

nature of the Z and R groups. Careful choice of RAFT agent, reactions conditions and monomer being polymerized is necessary to achieve good control over the polymerization and therefore well-defined polymeric products. Depending on the substituent group next to the C=S functionality, thiocarbonylthio can be divided into four groups; namely dithioesters, dithiocarbonates, trithiocarbonates and xanthates. The most effective RAFT agents are the dithioesters and trithiocarbonates which have carbon or sulfur atoms adjacent to the thiocarbonylthio group. For an efficient RAFT polymerization a) both the initial (A) and polymeric RAFT agent (Aa) should have a

reactive C=S double bond (high kadd), b) the intermediate radicals B and C should

fragment rapidly (high kβ, weak S-R bond) and give no side reactions, c) the

intermediate B should partition in favor of the products (kβ ≥ kadd) and d) the eliminated

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Figure 1.3. The structure of RAFT agent

The effectiveness of the RAFT agent depends on the monomer being polymerized and is determined by the properties of the free radical leaving group R and the group Z. Due to the fact that MAMs (more activated monomers) produce relatively more stabilized radicals, the Z-group has to be designed to help with the stabilization of the intermediate radical to favor radical addition on the C=S. Therefore, RAFT agents such as trithiocarbonates (Z = S-alkyl) or dithiocarbonates (Z = Ph) are commonly selected to control MAMs (MMA, St, MA). On the other hand, the high reactivity of LAMs (less activated monomers) make them poor homolytic groups, and they require intermediate radicals less stable, such as xanthates (Z = O-alkyl) or dithiocarbonates (Z = N-alkyl), in order to favor fragmentation of the propagating

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radical, as a more stable intermediate acts as radical sink and limits the

polymerization.122_{The guidelines for the proper RAFT agent for various monomers}

polymerization is presented in Figure 1.3.122, 123

Figure 1.3. Guidelines for selection of RAFT agents [Z–C(=S)S–R] for various

polymerizations. 122, 123

RAFT polymerization is perhaps the most versatile RDPR, and numerous

31 reported the seed polymerization of styrene in emulsion polymerization using cumyl dithiobenzene as a RAFT agent, finding that due to the limited transport of the RAFT agent from monomer droplets to polymer particles, a broad molecular weight distribution was obtained. Miniemulsion polymerization avoids transport issues and

has been utilized with a wide range of monomers such as styrene,125-128 _n-butyl

acrylate,129-131 _{methyl methacrylate,}132-134 _{n-butyl methacrylate,}125, 129, 133 _{as well as to}

synthesize di/tri-block copolymers.130, 132, 135 _{A problem that often appeared in the early}

literature was the lack of the colloidal stability of the system during the miniemulsion

polymerization.125, 133 _{In an attempt to shed light on this issue, Luo et al}136 _{used the}

theory developed by Ugelstad et al137 _{on the effect of low molecular weight water}

insoluble compounds on the swelling of the particles with monomer. Ugelstad et al137

theoretically and experimentally demonstrated that those low molecular weight compounds tremendously increased the swelling of the particles by monomers. The oligomers formed at low conversion in RAFT miniemulsion polymerization can act as

swelling agents. Luo et al136 _{proposed that the statistical distribution of these oligomer}

at the beginning of the RAFT polymerization led to their uneven distribution amount the monomer droplets and monomer diffused from the droplets devoid of oligomers to those containing oligomer. This would increase the size of the droplets with oligomer and decrease that of the droplets without oligomer, which in turn would accelerate the

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transport of monomer to the droplets containing oligomers. The word super-swelling has been coined to describe this system. The idea is appealing and it has been widely accepted as the cause of the stability problems in RAFT miniemulsion polymerization.

However, a close look into the calculations presented by Luo et al136 _{shows that what}

this article really shows is that super-swelling cannot occur in most of the real cases. In order to super-swelling to occur both small droplets size and high droplet water interfacial tensions are needed. For a droplet as small as 60 nm in diameter super- swelling does not occur if the interfacial tension is less or equal than 20 mN/m (Figure 2 in reference 136). On the other hand, for an interfacial tension as high as 25 mN/m, super-swelling does not occur for the particles sizes of 100 nm or larger (Figure 3 in reference 136). Considering that in the presence of surfactants the interfacial tensions are in the range of 5-10 mN/m and that the particles size of most miniemulsion above 100 nm, what Luo et al showed is that superswelling cannot be the case of the lack of colloidal stability of early works on the RAFT miniemulsion polymerization. Actually, no problems of the stability were found in this Thesis for the RAFT (Chapter 4) and nitroxide mediated (Chapter 5) polymerization and high solids content (52 wt%)

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