| Abstract: | Fluorocarbon ether bis(o-aminophenol) monomers were prepared by a multistep synthetic route based on the copper-promoted coupling of 4-iodophenyl acetate with 1,8-diiodoperfluoro-3,6-dioxaoctane, 1,11-diiodoperfluoro-3,9-dioxaundecane, 1,14-diiodoperfluoro-5,10-dimethyl-3,-6,9,12-tetraoxatetradecane, and 1,17-diiodoperfluoro-3,6,9,15-tetraoxaheptadecane. Acetic acidpromoted polycyclocondensations of the monomers with long-chain fluorocarbon ether-diimidate esters and -dithioimidate esters led to linear fluorocarbon ether-bibenzoxazole polymers soluble in 1,1,1,3,3,3-hexafluoroisopropanol and 1,1,2-trichloro-1,2,2-trifluoroethane. Polymer structures were verified by elemental and infrared spectral analysis. The polymers were rubbery gums and could be obtained in the inherent viscosity range of 0.20–0.79 dlg?1. Selection of monomers governed the glass transition temperatures of the resultant polymers. As expected, the polymers exhibited lower glass transition temperatures with increased fluorocarbon ether content, a minimum value of ?58°C being achieved. None of the polymers exhibited crystalline melt temperatures. Based on thermogravimetric analysis data, the thermooxidative stability of the polymers tended to decrease with increased fluorocarbon ether content. Onset of breakdown during thermogravimetric analysis in air occurred in the 350–400°C range. Isothermal aging of the polymers in air indicated good thermooxidative stability at 260°C; only 5% weight loss was recorded after 200 hr. |
