Styrene stable free radical polymerization

Figure 10. Styrene stable free radical polymerization scheme.

Finally, the use of stable free radical polymerization techniques in supercritical C02 represents an exciting new topic of research. Work in this area by Odell and Hamer involves the use of reversibly terminating stable free radicals generated by systems such as benzoyl peroxide or AIBN and 2,2,6,6-tetramethyl-l-piperidinyloxy free radical (TEMPO) [94], In these experiments, styrene was polymerized at a temperature of 125 °C and a pressure of 240-275 bar C02. When the concentration of monomer was low (10% by volume) the low conversion of PS which was produced had a Mn of about 3000 g/mol and a narrow MWD (PDI < 1.3). NMR analysis showed that the precipitated PS chains are primarily TEMPO capped, and the polymer could be isolated and then subsequently extended by the addition of more styrene under an inert argon blanket. The authors also demonstrated that the chains could be extended... 

The first workable capping agents for controlled radical polymerization were discovered by Rizzardo et al. [77, 78] who used nitroxides. The nitroxide reacts reversibly with radical chain ends but itself does not initiate the monomer. They called their new system Stable Free Radical Polymerization (SFRP). Scheme 32a depicts an example of SFRP using TEMPO (2,2,6,6-tetramethyl-1-piperidinyloxy). SFRP was developed independently by Georges at Xerox for the synthesis of styrene block polymer as dispersing agents [79]. 

A stable free radical polymerization using 2,2,6,6-tetramethyl-l-piperidinyloxy with maleic anhydride and styrene was used to prepared moderate molecular weight copolymers with polydispersities less than 1.5. Thermal re-activation of these copolymers in the presence of other monomers produced block polymers. 

The controlled emulsion polymerization of styrene using nitroxide-mediated polymerization (NMP), reversible addition-fragmentation transfer polymerization (RAFT), stable free radical polymerization (SFR), and atom transfer radical polymerization (ATRP) methods is described. The chain transfer agent associated with each process was phenyl-t-butylnitrone, nitric oxide, dibenzyl trithiocarbonate, 1,1-diphenylethylene, and ethyl 2-bromo-isobutyrate, respectively. Polydispersities between 1.17 and 1.80 were observed. 

Controlled Polymerization of Styrene Using 1,1-Diphenylethylene as Controlling Agent [Stable Free Radical Polymerization SFR]... 

Random copolymers of styrene/isoprene and styrene/acrylonitrile were prepared by the stable free radical polymerization process. The molecular weight of the polymers increased as a function of conversion, as expected for a living radical polymerization. The microstructure of the copolymers and reactivity ratios of the monomers were found to be very similar to what would be obtained for a conventional free radical polymerization. The propagating living radical chain reacts similarly to a conventionally propagating chain. 

Random copolymers of styrene/isoprene and styrene/acrylonitrile have been prepared by stable free radical polymerization. By varying the comonomer mole fractions over the range 0.1-0.9 in low conversion SFRP reactions it has been demonstrated that the incorporation of the two monomers in the copolymer is analogous to that found in conventional free radical copolymerizations. The composition and microstructure of random copolymers prepared by SFRP are not significantly different from those of copolymers synthesized conventionally. These two observations support the conclusion that the presence of nitroxide in the SFR process does not influence the monomer reactivity ratios or the stereoselectivity of the propagating radical chain. Rather, the SFR propagation mechanism is essentially the same as that of the conventional free radical copolymerization process. 

An approach similar to the previous divergent grafting-from method also served to synthesize dendrigraft poly(L-lysine) by ring-opening polymerization [111], styrene homopolymers and styrene-methacrylate copolymers by a combination of stable free-radical polymerization and atom transfer radical polymerization (ATRP) [112], and copolymers of 2-hydroxyethyl methacrylate with styrene or ferf-butyl methacrylate by ATRP [113]. 

Careful and extensive investigations of these nitroxide-mediated polymerizations (also referred to as stable free radical polymerization) have established optimum conditions for controlled radical polymerization of a variety of vinyl monomers (Matyjaszewski, 1998,2000). Variables examined include the structure of the nitroxide and the presence of other additives to control spontaneous polymerization of monomers such as styrene. It is noteworthy that in place of alkoxyamine initiators, a mixture of a normal free radical initiator such as an azo compound or a peroxide can also be used. 

In the 1990s the groups of Rizzardo and Georges reported a stable free radical polymerization process (SFRP) allowing the preparation of polystyrene with a narrow polydispersity. In the presence of stable free radicals, such as the mainly used 2,2,6,6-tetramethylpiperidine-A-oxyl (TEMPO), macromolecules based on styrene and styrene derivatives with well defined structures were synthesized [263,264],... 

Pasquale AJ, Long TE. Real-time monitoring of the stable free radical polymerization of styrene via in-situ mid-infrared spectroscopy. Macromolecules 1999 32 7954-7957. 

MacLeod RP, Veregin N, Odell PG, Georges MK. Electron spin resonance studies of the stable free-radical polymerization of styrene. Macromolecules 1998 31 530-531. 

The stable free radical polymerization technique is characterized by the growing polymer chains that are reversibly capped by a stable free radical [e.g., 2,2-tetramethyl-l-piperidynyloxy nitroxide (TEMPO)]. For example, stable polystyrene dispersions were prepared by the stable free radical polymerization of styrene conducted in miniemulsion polymerization at 135 C [62]. Sodium dodecylbenzene sulfonate, hexadecane, and potassium persulfate/ TEMPO were used as the surfactant, costabihzer, and initiator system, respectively. Prodpran et al. [63] studied the styrene miniemulsion polymerization stabilized by Dowfax 8390 and hexadecane and initiated by benzoyl peroxide at 125 °C. A molar ratio of TEMPO to benzoyl peroxide equal to 3 to 1 resulted in polystyrene with the lowest polydispersity index (1.3) of polymer molecular weight distribution. 

A bewildering array of names are used to describe the various controlled/living radial polymerization techniques currently in use. These include stable free radical polymerization (SFRP) [35-38], nitroxide mediated polymerization (NMP) [39], atom transfer radical polymerization (ATRP) [40-42 ] and degenerate transfer processes (DT) which include radical addition-fragmentation transfer (RAFT) [43, 44] and catalyst chain transfer (CCT). These techniques have been used to polymerize many monomers, including styrene (both linear and star polymers) acrylates, dienes, acrylamides, methacrylates, and ethylene oxide. Research activity in this field is currently expanding at a very high rate, as is indicated by the many papers published and patents issued. 

Most of the LFRP research ia the 1990s is focused on the use of nitroxides as the stable free radical. The main problems associated with nitroxide-mediated styrene polymerizations are slow polymerization rate and the iaability to make high molecular weight narrow-polydispersity PS. This iaability is likely to be the result of side reactions of the living end lea ding to termination rather than propagation (183). The polymerization rate can be accelerated by the addition of acids to the process (184). The mechanism of the accelerative effect of the acid is not certain. 

The presence of stable free radicals in the resin was further suggested by the strong inhibiting effect of traces of this product on the thermal polymerization of styrene. 

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