TEMPERATURE DEPENDENCE OF THE FLUORESCENCE SPECTRA OF LADDERLIKE POLYPHENYLSILSESQUIOXANE AND LADDERLIKE 1,4-PHENYLENE-BRIDGED POLYVINYLSILOXANE

摘要

Fluorescence spectra of ladderlike polyphenylsilsesquioxane (LPPS) and ladderlike 1,4-phenylene-bridged polyvinylsiloxane (LPPVS) have been measured as a function of temperature (4-55℃), in dilute tetrahydrofuran solution.The excimer (IE) to monomer (IM) intensity ratio (IE/IM) of LPPS dilute solution shows a double linear Arrhenius plot with a break point ascribable to a transition temperature Tr. This behavior has not been found for single chain polyorganosiloxanes.When In/E of LPPS was plotted against 1/T, it also gave a double linear plot with one break point, which was found in single chain polyorganosiloxanes. The different behaviors between LPPS and single chain polyorganosiloxanes may be mainly attributed to the relatively rigid double-chain macromolecular backbone of LPPS. However, the ln(IE/IM) of dilute LPPVS solution versus 1/T shows a simple linear variation with a positive slope which confirms our proposition. The difference between the fluorescence results of LPPS and those of LPPVS may possibly derive from their structure differences and cooperative motion in backbone chain bonds.