Three different synthetic methods were studied with respect to their usefulness for the preparation of poly(isosorbide carbonate) (PIC). Thermal polycondensations of isosorbide with dimethyl-or diethyl carbonate in bulk proved unsuccessful, regardless of the transesterification catalyst. Polycondensations of isosorbide with diphosgene in pyridine gave polycarbonates, the molecular weights of which depended largely on the excess of diphosgene. In all experiments, OH-terminated linear chains were the main products. Similar results were obtained from pyridine-promoted phosgenations in dioxane. However, polycondensations of equimolar mixtures of isosorbide and isomannide mainly yielded cyclic polymers. Pyridine-promoted polycondensations of isosorbide with isosorbide bischloroformate only gave low molar mass polycarbonates. At low temperatures, even-numbered linear chains were the main products, but higher temperatures gave even-numbered cycles. SEC measurements with triple detection evidenced the formation of high molar mass polycarbonates in the phosgenation experiments and a Mark-Houwink equation was elaborated. The glass transition temperatures varied between 115 and 165 °C depending on the molar mass.

Isosorbide and equimolar amounts of various diols were polycondensed with diphosgene and pyridine. Bisphenol A, 3,3′‐dimethyl bisphenol A, bisphenol C, 1,3‐bis(4‐hydroxybenzoyloxy)propane, and 1,4‐cyclohexane diol were used as comonomers. The compositions were determined by 1H NMR spectroscopy; the random sequences were characterized by 13C NMR spectroscopy. For the high‐molar‐mass copolycarbonates of bisphenol A, 3,3′‐dimethyl bisphenol A, and bisphenol C, matrix‐assisted laser desorption/ionization time‐of‐flight mass spectrometry proved that the chain growth was mainly limited by cyclization. Copolycarbonates with alternating sequences were obtained by the polycondensation of bisphenol A with isosorbide bischloroformiate or from isosorbide and bisphenol A bischloroformiate. In these cases, large amounts of cyclic oligo‐ and polycarbonates were also formed. The glass‐transition temperatures were determined by differential scanning calorimetry measurements. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 3616–3628, 2006

The homopolyester of isosorbide and cis–trans 1,4‐cyclohexane dicarboxylic acid (CHDA) was prepared by three different methods, but only polycondensation of isosorbide and CHDA dichloride yielded a satisfactory molecular weight (corrected $\overline M _{\rm n} $ = 11 000 Da). For the best sample the MALDI‐TOF mass spectrum revealed a high content of cycles. The homopolyester of CHDA and isomannide or isoidide was prepared analogously. For the homopolyesters of CHDA high glass transition temperatures were found (Tg = 146 °C for isosorbide, 133 °C for isomannide, and 115 °C for isoidide), whereas the polyester of isosorbide and succinic acid (SuA) has a Tg around 77 °C. Copolyester of isosorbide and various molar ratios of CHDA and SuA were prepared by two different methods, but only rather low molecular weights were obtained. SEC measurements with and without “universal calibration” revealed that the normal calibration with polystyrene overestimates the real molecular weights by 30–45%.magnified image

Numerous polycondensations of isosorbide and suberoyl chloride or other aliphatic dicarboxylic acid dichlorides were performed with pyridine as a catalyst and HCl acceptor. The reaction conditions were varied to optimize both the molecular weight and the fraction of cyclic oligo‐ and polyesters. Furthermore, we attempted to obtain the cyclic monomer by catalyzed back‐biting degradation of the molten cyclic polyesters above 220 °C in vacuo. The polyesters were characterized by viscosity and size exclusion chromatographic measurements as well as matrix‐assisted laser desorption/ionization time‐of‐flight mass spectrometry. In selected cases, mixtures of linear and cyclic polyesters were treated with a hot solution of partially methylated β‐cyclodextrin in methanol. This treatment allowed for a selective extraction of the linear chains up to approximately 5000 Da. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 3414–3424, 2003