RAFT polymerization reactions

FIGURE 5.19 Examples of glycomonomers used in RAFT polymerization reactions. 

Other examples of RAFT polymerization reactions under microwave irradiation can be found in the literature. ... 

Other radical reactions not covered in this chapter are mentioned in the chapters that follow. These include additions to systems other than carbon-carbon double bonds [e.g. additions to aromatic systems (Section 3.4.2.2.1) and strained ring systems (Section 4.4.2)], transfer of heteroatoms [eg. chain transfer to disulfides (Section 6.2.2.2) and halocarbons (Section 6.2.2.4)] or groups of atoms [eg. in RAFT polymerization (Section 9.5.3)], and radical-radical reactions involving heteroatom-centered radicals or metal complexes [e g. in inhibition (Sections 3.5.2 and 5.3), NMP (Section 9.3.6) and ATRP (Section 9.4)]. 

The processes described in this section should be contrasted with RAFT polymerization (Section 9.5.3), which can involve the use of similar thioearbonylthio compounds. A. A -dialkyl dithiocarbamates have very low transfer constants in polymerizations of S and (mctb)acrylatcs and arc not effective in RAFT polymerization of these monomers. However, /V,A -dialkyl dithiocarbamates have been successfully used in RAFT polymerization of VAc. Certain O-alkyl xanthates have been successfully used to control RAFT polymerizations of VAc, acrylates and S. The failure of the earlier experiments using these reagents and monomers to provide narrow molecular weight distributions by a RAFT mechanism can he attributed to the use of non-ideal reaction conditions and reagent choice. A two part photo-initiator system comprising a mixture of a benzyl dithiocarhamate and a dithiuram disulfide has also been described and provides better control (narrower molecular weight distributions).43... 

Macromonomer RAFT polymerization is most effective with methacrylate monomers (Table 9.9).With monosubstituted monomers (e.g. S, acrylates) graft copolymerization, is a significant side reaction which can be mitigated but not eliminated by the use of higher reaction temperatures. 

Although the term RAFT (an acronym for Reversible Addition-Fragmentation chain Transfer)38" is sometimes used in a more general sense, it was coined to describe, and is most closely associated with, the reaction when it involves thiocarbonylthio compounds. RAFT polymerization, involving the use of xanthates, is also sometimes called MADIX (Macromolccular Design by Interchange of Xambate) 96 The process has been reviewed by Rizzardo et [Pg.502]

Various side reactions may complicate RAFT polymerization. Transfer to solvents, monomer and initiator occur as in conventional radical polymerization. Other potential side reactions involve the intermediate radicals 165 and 167. These radicals may couple with another radical (Q ) to form 271 or disproportionate with Q to form 270. They may also react with oxygen. The intermediate radicals 165 and 167 are not known to add monomer. 

Polymers with primary or secondary amine functionality cannot be prepared directly by RAFT polymerization these groups undergo facile reaction with thiocarbonylthio compounds. Such polymers can be prepared indirectly using RAFT agents with latent amine functionality, such as the phthalimido group in... 

Many block and graft copolymer syntheses involving transformation reactions have been described. These involve preparation of polymeric species by a mechanism that leaves a terminal functionality that allows polymerization to be continued by another mechanism. Such processes are discussed in Section 7.6.2 for cases where one of the steps involves conventional radical polymerization. In this section, we consider cases where at least one of the steps involves living radical polymerization. Numerous examples of converting a preformed end-functional polymer to a macroinitiator for NMP or ATRP or a macro-RAFT agent have been reported.554 The overall process, when it involves RAFT polymerization, is shown in Scheme 9.60. 

By utilizing a combination of RAFT and cationic ROP, the synthesis of [poly(methyl methacrylate)][poly(l,3-dioxepane)][polystyrene] miktoarm star terpolymers was achieved [182], The approach involved the synthesis of PS functionalized with a dithiobenzoate group by RAFT polymerization and subsequent reaction with hydroxyethylene cinnamate (Scheme 98). The newly created hydroxyl group was then used for the cationic ring opening polymerization of 1,3-dioxepane (DOP). The remaining dithiobenzoate group was used for the RAFT polymerization of methyl methacrylate. 

Reverse transcriptase, 21 281 Reverse water-gas shift reactions, 5 14-15 Reversible addition-fragmentation chain transfer (RAFT), 7 621, 623 Reversible addition-fragmentation chain transfer (RAFT) polymerization,... 

While in most of the reports on SIP free radical polymerization is utihzed, the restricted synthetic possibihties and lack of control of the polymerization in terms of the achievable variation of the polymer brush architecture limited its use. The alternatives for the preparation of weU-defined brush systems were hving ionic polymerizations. Recently, controlled radical polymerization techniques has been developed and almost immediately apphed in SIP to prepare stracturally weU-de-fined brush systems. This includes living radical polymerization using nitroxide species such as 2,2,6,6-tetramethyl-4-piperidin-l-oxyl (TEMPO) [285], reversible addition fragmentation chain transfer (RAFT) polymerization mainly utilizing dithio-carbamates as iniferters (iniferter describes a molecule that functions as an initiator, chain transfer agent and terminator during polymerization) [286], as well as atom transfer radical polymerization (ATRP) were the free radical is formed by a reversible reduction-oxidation process of added metal complexes [287]. All techniques rely on the principle to drastically reduce the number of free radicals by the formation of a dormant species in equilibrium to an active free radical. By this the characteristic side reactions of free radicals are effectively suppressed. 

The temperature optimization for the RAFT polymerization of EAA revealed an optimum reaction temperature of 70 °C. Block copolymers with a poly(methyl acrylate) (PMA), a poly(n-butyl acrylate) (PnBA), a PMMA, or a poly(A,A-dimethyl aminoethyl methacrylate) (PDMAEMA) first block and a poly(l-ethoxyethyl acrylate) (PEEA) second block were successfully synthesized in an automated synthesizer. The synthesis robot was employed for the preparation of 16 block copolymers consisting of 25 units of the first block composed of PMA (exp. 1 ), PnBA (exp. 5-8), PMMA (exp. 9-13), and PDMAEMA (exp. 13-16) and a second block of PEEA consisting of 25, 50, 75, or 100 units, respectively. The first blocks were polymerized for 3 h and a sample from each reaction was withdrawn for SEC analysis. Subsequently, EAA was added and the reactions were continued for 12 h. The molar masses and PDI values of the obtained block copolymers are shown in Fig. 15. 

NMP is as successful as RAFT polymerization for the construction of block copolymers. A small library of block copolymers comprised of poly(styrene) (PSt) and poly(ferf-butyl acrylate) (FYBA) was designed and the schematic representation of the reaction is depicted in Scheme 10 [49]. Prior to the block copolymerization, the optimization reactions for the homopolymerization of St and f-BA were performed as discussed in this chapter (e.g., see Sect. 2.1.2). Based on these results,... 

Reversible addition-fragmentation chain transfer (RAFT) polymerization using 2,2 -azobisisobutyronitrile and either A, A-dimethyl-5-thiobenzoylthiopropionamide or A-dimethyl-5-thiobenzoylthioacetamide as chain transfer agents has been used to prepare low polydispersity poly(A, A-dimethylacrylamide). The chain transfer agents were unusually effective in suppressing free radical termination reaction, thereby mimicking a living polymerization reaction. 

If reactions 1 to 3 in Scheme 7 are considered, there is no reason to assume that addition of a RAFT agent to a conventional free radical polymerization will have an effect on the polymerization rate, since the equilibrium concentration of propagating radicals will not be affected. However, it has been found that considerable retardation does take place in RAFT polymerization [275-281]. The intermediate radical was postulated to be the reason for the significant retardation of the polymerization rate. Two explanations for retardation have been put forward ... 

Figure 5.11. Illustration of the general reaction scheme responsible for RAFT polymerization.

Nitroxide mediated SFRP, DPE mediated polymerization, ATRP, RAFT polymerization, etc. achieve polymerization control through the use of kinetic mediators or transfer agents, which protect a propagating free radical from imdesirable transfer and termination reactions. The emulsion block copolymer method is unique in that it does not require the use of any chemical mediators to achieve this control. Polymerization control is achieved by physically trapping radicals by... 

The proposed reaction mechanism for RAFT polymerization under a constant source of y-radiation is shown in Scheme 3. The basic steps of the RAFT mechanism are extended by reaction steps that effect grafting onto polymeric surfaces. 

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