CYCLOPOLYMERIZATION OF BIS(FLUOROALKYL) DIPROPARGYLMALONATE DERIVATIVES AND CHARACTERIZATION OF THE PRODUCTS

Bis(2,2,2-trifluoroethyl) and bis(1,1,1,3,3,3-hexafluoro-2-propyl) dipropargylmalonate are polymerized by MoCl5-and WCl6-based catalysts to give new, high molecular weight polymers. High-polymer yield is obtained in the presence of MoCl5-based catalysts. When MoCl5-EtAlCl2 is used as a catalyst, the highest number-average molecular weights (M(n)) of poly[bis(2,2,2-trifluoroethyl) dipropargylmalonate] and poly[bis(1,1,1,3,3,3-hexafluoro-2-propyl) dipropargylmalonate] are found to be ca. 1.1 x 10(5) and 3.1 x 10(5), respectively. The products, dissolved in common organic solvents, can be cast into films. Mechanical, thermal, and electrical properties as well as gas permeabilities of the polymers are determined in an effort to elucidate their structures.