Stable free radical polymerization random copolymers

Functional Polymers Random Copolymers by Stable Free Radical Polymerization... 

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. 

Over the past few years there has been a tremendous interest in living radical polymerizations. One type of living radical polymerization is stable free radical polymerization, SFRP, where a stable free radical such as TEMPO (2,2,6,6-tetramethylpiperidinoxyl) is used to reversibly cap the growing polymer chain (L2). SFRP has the advantage over conventional radical polymerization in that the polymers prepared are living and can be used for further polymerization to make blocks or other complex architectures. The polymers prepared by the SFRP process have a narrower molecular weight distribution compared to polymers prepared by conventional radical polymerization in the case of block copolymers this may be a desirable attribute. This article focuses on the use of the SFRP process to prepare random copolymers. 

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. 

Free-radical polymerization mediated by stable nitroxyl radicals like TEMPO (2,2,6,6-tetramethylpiperidinyl-l-oxy) (Fig. 6.23) is a simple and robust method to synthesize homopolymers and random and block copolymers with narrow poly-dispersities and/or controlled chain architectures. A key to the success of this polymerization is believed to be the reversible combination of a polymer radical, P , with a stable nitroxyl radical, N, to form an adduct, P-N, which is a dormant species ... 

Poly(VPA-co-slyrene) has been obtained by free radical polymerization of styrene and dimethyl vinylphosphonate in the bulk, followed by hydrolysis." The resulting copolymers, shown in Scheme 13.1d, had a low VPA content (5-14 mol%). Despite the difference between the reactivity ratios of the comonomers, poly(slyrene-co-dimethyl vinylphosphonate) presented only a single glass transition temperature, indicating a near random connectivity between the styrene and dimethyl vinylphosphonate units in the copolymers. The copolymers were stable under air and inert atmosphere... 

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