Fluorescence methods in polymer science

Abstract

Various aspects of the application of fluorescence characteristics in the field of polymer research are described. The polarization characteristics of fluorescence, that is, the angular distribution of the intensity of the polarized component, are indicative of the distribution patterns of fluorescent molecules in the medium. This principle can be utilized for the investigation of molecular orientation behavior in polymer solids. Examples are given for the molecular orientation behaviors during the deformation of poly(vinyl alcohol) and polypropylene films. The phenomenon of rotational depolarization of fluorescence is applied to the measurement of micro-Brownian motions of polymer chains and the local viscosity of polymer solutions and melts. The internal structure of concentrated poly(styrene) solutions and the molecular motions in the melts of n-paraffins and polyethylene homologs are discussed. Rotational relaxation time ranging from 10−12 to 10−5 sec can be measured by this method by using the lifetime of excitation of fluorescent groups as the reference time scale. The phenomenon of the excimer fluorescence emitted from the excited dimer provides a new method for studying molecular configuration and conformation of polymer molecules. Examples are given for the case of naphthalenecontaining polymers. The sequence of monomeric units in copolymers of vinylnaphthalene and styrene are studied from the intensity of excimer fluorescence relative to that of ordinary fluorescence from the naphthalene groups. The intramolecular excimer formations of polymer molecules are also discussed in relation to molecular motions.