Solvent-Dependent Light-Induced Structures in Gem-Dichlorocyclopropanated Polybutadiene Solutions.

The formation of permanent structures upon mild red laser illumination in transparent polydiene solutions is examined in the case of gem-dichlorocyclopropanated polybutadiene ( gDCC-PB) polymers bearing 15% functional units of the dichlorocyclopropane groups. The response was found to be distinct from the precursor PB. Whereas fiber-like patterns were clearly observed in both precursor and gDCC-PB solutions in cyclohexane, these were absent in the case of gDCC-PB/chloroform but were present in the precursor PB/chloroform solutions. The involved mechanical stresses were not sufficient for the gDCC activation to be detected by NMR spectroscopy. Remarkably, addition of even 10 wt % gDCC-PB into the latter solution sufficed to suppress the light-induced patterning. The importance of the chemical environment on the response to light irradiation was further checked and confirmed by use of other PB copolymers. Different diameter patterns and kinetics were observed. The strong solvent and comonomer mediated effect was reflected neither in solvency nor in optical polarizability differences of the polymers solvent couples.