Some rheological properties of highly crosslinked polysiloxanes

Abstract

AbstractSeven crosslinked polydimethylsiloxanes were prepared from carboxyl‐terminated siloxane oligomers of different average lengths and a trifunctional imine. The 10‐sec torsion modulus was measured as a function of temperature, and compression‐deflection data were obtained on swollen specimens. Polymer‐solvent interaction parameters were calculated from equilibrium swelling ratios and modulus data. The plots of modulus versus temperature show two distinct transitions for all the crosslinked polymers. The low‐temperature transition corresponds to the siloxane chains, whereas the high‐temperature transition should be attributed to the portion of the network chain derived from the crosslinking agent and the organic part of the oligosiloxane. On shortening the siloxane blocks, both transitions shift to successively higher temperatures and higher modulus levels. However, the siloxane transition temperature shows only a limited rise even when the average block length becomes quite small. The low siloxane polymers seem to exhibit two swelling maxima, each corresponding to one of the constituents. The studied materials from nonrandom copolymeric structures typical of block polymers. Such microphase systems can probably be expected in crosslinked polymers whenever the crosslinking agent participates significantly in the network chains and its compatibility with the flexible chains species is poor.