Collect. Czech. Chem. Commun. 1998, 63, 1803-1814

Polymerization of Nitrophenyl and 3-Diethylaminophenyl Prop-2-yn-1-yl Ethers with PdCl2. Polymers and Copolymers Characterization

Hynek Balcara, Petr Hollerb, Jan Sedláčekc and Vratislav Blechtad

a J. Heyrovský Institute of Physical Chemistry, Academy of Sciences of the Czech Republic, 182 23 Prague 8, Czech Republic
b Institute of Macromolecular Chemistry, Academy of Sciences of the Czech Republic, 162 06 Prague 6, Czech Republic
c Department of Physical and Macromolecular Chemistry, Faculty of Sciences, Charles University, 128 40 Prague 2, Czech Republic
d Institute of Chemical Process Fundamentals, Academy of Sciences of the Czech Republic, 165 02 Prague 6-Suchdol, Czech Republic


2-, 3- and 4-Nitrophenyl prop-2-yn-1-yl ethers were polymerized with PdCl2 in N,N-dimethylformamide (DMF) giving brown polymers soluble in DMF, dimethyl sulfoxide and N-methylpyrrolidone. Broad (mostly bimodal) molecular weight distributions were observed by size-exclusion chromatography (SEC) with maxima at molecular weight of about 4 . 103 and 1 . 105. With the same catalyst, 3-diethylaminophenyl prop-2-yn-1-yl ether gave predominantly low molecular weight homopolymer (Mn = 4 200) soluble in DMF, N-methylpyrrolidone, CHCl3 and tetrahydrofuran-soluble copolymers with 4-nitrophenyl prop-2-yn-1-yl ether (Mn about 3 000). IR, NMR and UV-VIS spectra of prepared polymers and copolymers proved the structure to consist of the polyene-type main chain with phenoxymethyl pendant groups bearing nitro or diethylamino substituents.

Keywords: Propargyl ethers; Palladium dichloride; Polymerization; Copolymerization; Polyacetylenes; Homogeneous catalysis.