Small angle x‐ray studies of siloxane‐urea segmented copolymers

Novel segmented copolymers were synthesized using aminopropyl terminated linear poly(dimethylsiloxane) oligomers as the soft component and various diisocyanates as the hard segments. As a result of the large differences in the cohesive energy density (solubility parameter) between the two components, phase separation occurs to form a microdomain structure at relatively low oligomer molecular weights. Since chain extenders were not employed during the synthesis, the “hard” segments are strictly related to the length of the diisocyanate moiety utilized in the reaction, In this paper we utilize these copolymers as reasonable models for investigating the various methods available for determining the interfacial layer thickness between the hard and soft phase. Specifically, in these systems there is no hard segment length distribution as is the usual case for segmented urethanes. Utilizing Porod's law, and appropriate analysis, both positive and negative deviations were found in the systematic series of copolymers. The degree of positive and negative character was found to be dependent upon copolymer composition. Negative deviations were accounted for in terms of a finite interfacial thickness, which turned out to be relatively small as anticipated, while the positive deviations were assigned to isolated hard segments that reside within the soft segment matrix, i.e., concentration fluctuations. In calculating the interfacial thickness, several methods were applied and in general, close agreement was obtained. Finally, correlation function analysis in conjunction with determination of the coherent Porod lengths, etc. were determined and discussed accordingly. Cautionary comments are also provided for researchers who apply less complete small angle x‐ray scattering (SAXS) analysis to related block or segmented copolymers with regard to phase separation behavior.