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Methyl methacrylate (MMA)/N,N-dimethyl acrylamide (DMA) gradient copolymers with various chemical composition were synthesized by nitroxide-mediated controlled radical polymerization (NMP). Molecular weight (MW) characterization via gel permeation chromatography demonstrated that these materials were made in a “controlled” manner. The reactivity ratios values r1(MMA) = 2.36 and r2(DMA) = 0.33 were experimentally determined using the linear least-squares numerical method, results in good agreement with the literature. Characterization of the glass transition temperature, Tg, by differential scanning calorimetry (DSC) of gradient copolymers exhibited one Tg, with a value intermediate to the Tg of pure poly(methyl methacrylate) (PMMA) and poly(N,N-dimethyl acrylamide) (PDMA). In contrast, di- and triblock copolymers made of poly(n-butyl acrylate) (PBA) as central block and PMMA/PDMA gradient copolymer as external block yielded two Tg, one corresponding to the Tg of PBA and the other intermediate to the Tg of...

Nanostructured thermosets may be obtained by self-assembly of amphiphilic block copolymers in a reactive solvent and fixation of the morphologies by the cross-linking reaction. Nanostructuration requires the presence of a bock that remains miscible in the polymer during polymerization. The selection of the miscible block depends on the particular system and in some cases (e.g., for epoxy-amine network based on diglycidyl ether of bisphenol A, and 4,4'- diaminodiphenylsulfone) it is very difficult to find such a block. In this manuscript it is shown that random copolymers of methyl methacrylate (MMA) and N,N-dimethylacrylamide (DMA) containing different molar fractions of DMA, can be used as a miscible block for the nanostructuration of epoxies. The miscibility of the random copolymer during formation of the epoxy network was first analyzed determining cloud-point conversions as a function of the molar fraction of DMA in the copolymer. A thermodynamic model of the phase separation was performed using the Flory-Huggins model and taking the polydispersities of both polymers into account. A single expression of the interaction parameter based on the theory of random copolymers provided a reasonable fitting of the experimental cloud-point curves. The significant increase in the miscibility produced by using small DMA molar fractions in the copolymer was explained by the high negative value of the binary interaction energy between DMA and the epoxy-amine solvent, associated to the positive value of the interaction energy between DMA and MMA units. Block copolymers with poly(n-butyl acrylate) as the immiscible block and the random copolymer P(MMA-co-DMA) as the miscible block were used for the nanostructuration of epoxy networks. The necessary molar fraction of DMA in the miscible block to stabilize a dispersion of nanosize domains depended on the fraction of the immiscible block., Comment: Author's version of a published article, available at Macromolecules (ACS), http://pubs.acs.org/doi/abs/10.1021/ma062185l