Molar mass distribution of a commercial aliphatic hyperbranched polyester based on 2,2-bis(methylol)propionic acid

The determination of absolute molar mass averages (MMA) and molar mass distribution (MMD) of the fourth generation hyperbranched polyester Boltorn H40 (Perstorp Specialty Chemicals AB), synthesized from 2,2-bis(methylol)propionic acid (bis-MPA) as the AB2 monomer and ethoxylated pentaerythritol as the B4 core molecule was studied in dependence on the type of solvent, preparation procedure and solution concentration. Due to a large number of polar hydroxyl groups, ester, and also some residual carboxyl groups, a very stable H-bond network is formed at room temperature, that can-not be completely disrupted by dissolving the sample in solvents such as tetrahydrofuran (THF), N,N-dimethylacetamide (DMAc), a mixture of THF and methanol (9:1, v/v), and a solution of 0.7% LiBr in DMAc. The H-bonds between the polar groups break down completely and the dissolution of Boltorn H40 on the molecular level is achieved only when the sample is thermally pretreated at a minimum 140 °C for at least 20 min prior to dissolution in solvents THF/methanol or LiBr/DMAc. Thus, determined MMA and molar mass distribution (MMD) of Boltorn H40 are independent on the kind of the solvent and solution concentration.