Synthesis of Unsymmetrically .alpha.-Substituted Poly(dipropargyl ether) Derivatives by Metathesis Catalysts

Abstract

Soluble and unsymmetrically cyclized poly(dipropargyl ether) derivatives bearing α-substituents were synthesized and characterized. The monomers were propargyl α-substituted (methyl, pentyl, methyl phenyl, cyclohexyl) propargyl ethers. Polymerizations were carried out with transition metal catalysts. It was found that MoCl 5 -based catalysts were very effective for the cyclopolymerization of α-substituted dipropargyl ethers. The solubility of poly(dipropargyl ether)s was remarkably improved by incorporation of α-substituent groups. The resulting polymers exhibited good solubility in common organic solvents such as tetrahydrofuran, chloroform, DMF. The structure of the products was confirmed by IR, UV-visible, and 1 H- and 13 C-NMR spectroscopy. All of the polymers were amorphous, reddish solids and their weight average molecular weights were in the range of 24.3 x 10 3 -73 x 10 3 . The oxidative stability was dependent on the α-substituent groups of the poly(dipropargyl ether)s. The electrical conductivities of iodine-doped poly(dipropargyl ether) derivatives were 10 -4 -10 -2 s/cm.