The fractal dimension of a macromolecular coil is used for the characterization of a polymeric melt structure. It is shown that the kinetics of oxygen consumption is defined by both the chemical constitution of a polymer and its structure. The quantitative analysis of the kinetical curves of the oxygen consumption in the thermooxidative degradation process was carried out in the framework of the fractal approach. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 2378–2381, 2003

An innovative thermal transesterification protocol for the synthesis of linear and alkylene carbonates was investigated under both batch and continuous-flow (CF) conditions. Accordingly, model 1,n-diols (n = 2–4) and glycerol were set to react with dimethyl carbonate (DMC) at T and p of 150–260 °C and 1–50 bar, respectively, in the absence of any catalyst. 1,2-diols afforded the corresponding five-membered ring carbonates as the main products with a quantitative conversion and a selectivity up to 94%, whereas 1,3-diols gave the six-membered ring products along with linear mono- and dicarbonate derivatives. A complete conversion was attained also for glycerol, but the products distribution depended on reaction conditions: the CF mode allowed the synthesis of glycerol carbonate, whereas batch reactions yielded either glycerol carbonate or its derivative from a further transesterification reaction, i.e., methyl (2-oxo-1,3-dioxolan-4-yl)­methyl carbonate. The selectivity toward these two compounds was in the range of 83%–94%. An addition of gaseous CO2 (up to 20 bar) allowed to control further the selectivity of batch reactions.

At 90-120 °C, in the presence of methylcarbonate and bicarbonate methyltrioctylphosphonium salts as catalysts ([P8881][A]; [A] = MeOCO2 and HOCO2), the transesterification of non-toxic dimethyl- and diethyl-carbonate (DMC and DEC, respectively) with 1,X-diols (2 ≤ X ≤ 6) proceeds towards the formation of cyclic and linear products. In particular, 1,2-propanediol and ethylene glycol afford propylene- and ethylene-carbonate with selectivity and yields up to 95 and 90%, respectively; while, the reaction of DMC with higher diols such 1,3-butanediol, 2-methyl-1,3-propanediol, 1,3-propanediol, 2,2-dimethyl, 1,3-propanediol, 1,4-butanediol and 1,6-hexanediol produce linear C8-C10 dicarbonates of general formula MeOC(O)O∼∼∼OC(O)OMe as the almost exclusive products. Of note, these dicarbonate derivatives are not otherwise accessible in good yields by other conventional base catalyzed methods. Among 1,3-diols, the only exception was 2-methyl 2,4-pentandiol that yields the corresponding cyclic carbonate, i.e. 4,4,6-trimethyl-1,3-dioxan-2-one. In no one case, polycarbonates are observed. Such remarkable differences of product distributions are ascribed to the structure (branching and relative position of OH groups) of diols and to the role of cooperative (nucleophilic and electrophilic) catalysis which has been proved for onium salts. The investigated carbonate salts are not only effective in amounts as low as 0.5 mol%, but they are highly stable and recyclable.

Methyl trioctylphosphonium methyl carbonate [P(8881)](+)[MeOCO(2)](-) was prepared by the alkylation of trioctyl phosphine with the non-toxic dimethyl carbonate. This salt was a convenient source to synthesize different ionic liquids where the methyl trioctylphosphonium cation was coupled to weakly basic anions such as bicarbonate, acetate, and phenolate. At 90-220 °C, all these compounds [P(8881)](+)X(-); X = MeOCO(2); HOCO(2); AcO; PhO were excellent organocatalysts for the transesterification of dimethyl and diethyl carbonate with primary and secondary alcohols, including benzyl alcohol, cyclopentanol, cyclohexanol, and the rather sterically hindered menthol. Conditions were optimized to operate with very low catalyst loadings up to 1 mol% and to obtain non-symmetric dialkyl carbonates (ROCO(2)R'; R = Me, Et) with selectivity up to 99% and isolated yields >90%. The catalytic performance of the investigated ionic liquids was discussed through a cooperative mechanism of simultaneous activation of both electrophilic and nucleophilic reactants.