Cyclopolymerization of difluoroalkyl dipropargyl-malonate derivatives and characterization of the products

Abstract

This dissertation deals with the cyclopolymerization of dipropargyl malonate derivatives containing fluorinated compounds. In the polymerization of these dipropargyl malonate derivatives, $MoCl_5$ is more effective catalyst than $WCL_6$. $EtAlCl_2$ and n-$Bu_4Sn$ exhibit no catalytic activity in the polymerization of the present monomers. On the other hand, $EtAlCl_2$ hardly affects the polymer yield, but its presence leads to higher number average molecular weights. When $MoCl_5-EtAlCl_2$ is used as a catalyst, the highest number average molecular weights of poly [bis(2,2,2-trifluoroethyl)-, poly-[bis(1,1,1,3,3,3-hexafluore-2-propyl)-, and poly [bis(heptafluorobutyl) dipropargylmalonate] are found to be ca. 1.1X105, 3.1X105, and 2.75X105, respectively. The product polymer are black, soluble, and thermally stable solid. The cyclopolymers obtained in this study are mainly amorphous. Compared against poly(DEDPM), it is found that the present polymers are soft and ductile. The electrical conductivities of $I_2$-doped polymers are in the range of 10-2-10-3. The $PO_2$ values and separation factors($PO_2/PN_2$) of the product polymer are in the range of 3$\times$10-10-3.9$\times$10-8[cm3 (STP), cm/cm2.sec.cmHg], 1.7-2.4, respectively.