Structural properties of poly(propylene oxide) from diffraction experiments and reverse Monte Carlo simulation

Structural characteristics of an amorphous polymer melt, poly(propylene oxide) (PPO), have been studied by combining neutron and x-ray diffraction experiments and computer modeling using the reverse Monte Carlo (RMC) technique. The neutron diffraction experiments were performed on hydrogenous as well as deuterated samples. The experimentally determined nearest-neighbor distances were found to be in good agreement with literature data. The RMC modeling was applied for interpretation of the diffraction data to obtain more detailed structural information on bond angles, intermediate and long range correlations. For the intermediate range structure, the experimental structure factors demonstrate a first diffraction peak at about 1.45 Angstrom(-1), which from the RMC produced model can be related to the interchain distance of an almost random packing of the polymer chains. To investigate the chain conformation, partial atomic pair correlation functions have been calculated for atoms belonging to monomers close in sequence. The results show that the most probable conformation is a "stretched" trans conformation, where two consecutive methyl groups are pointing in almost opposite directions. Calculated bond and dihedral angle distributions support this finding and demonstrate the ability of the RMC method to produce polymer structures in good agreement with experimental results. (C) 1998 American Institute of Physics. [S0021-9606(98)52441-5].