Side-chain crystallization in alkyl-substituted cellulose esters and hydroxypropyl cellulose esters.

The differences in side chain crystallization behavior between cellulose esters (CEs) and hydroxypropyl cellulose esters (HPCEs) were systematically investigated by a combination of differential scanning calorimetry (DSC) and small and wide-angle X-ray scattering techniques. DSC investigation indicated that under the same side chain length, the fusion enthalpy and the number of crystallized CH2 of CEs were smaller than HPCEs. At the same time, their d-spacing and molecular arrangements were also different from each other. For the CEs, the side chains are perpendicular to the main chain, while the side chains most probably tend to tilt to main chain in the HPCEs as was evidenced by X-ray scattering results. The phenomenon can be understood as a consequence of different flexibility of attachment bridges in both kinds of side chain polymers and the steric hindrance of methyl group in the hydroxypropyl group in HPCEs. In addition, the added hydroxypropyl substituents make the side chain length increasing.