SYNTHESIS OF UNSYMMETRICALLY ALPHA-SUBSTITUTED POLY(DIPROPARGYL ETHER) DERIVATIVES BY METATHESIS CATALYSTS

Soluble and unsymmetrically cyclized poly(dipropargyl ether) derivativ es bearing alpha-substituents were synthesized and characterized. The monomers were propargyl alpha-substituted (methyl, pentyl, methyl phen yl, cyclohexyl) propargyl ethers. Polymerizations were carried out wit h transition metal catalysts. It was found that MoCl5-based catalysts were very effective for the cyclopolymerization of ex-substituted dipr opargyl ethers. The solubility of poly(dipropargyl ether)s was remarka bly improved by incorporation of alpha-substituent groups. The resulti ng 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 H-1- and C-13-NMR spectroscopy. All of the polymers were amorphous, reddish solids and their weight averag e molecular weights were in the range of 24.3 x 10(3)-73 x 10(3). The oxidative stability was dependent on the alpha-substituent groups of t he poly(dipropargyl ether)s. The electrical conductivities of iodine-d oped poly(dipropargyl ether) derivatives were 10(-4)-10(-2) s/cm.