화학공학소재연구정보센터
Journal of Molecular Catalysis A-Chemical, Vol.169, No.1-2, 63-66, 2001
Transition metal acetylide catalysts for polymerization of alkynes 2. Effect of ligands on catalytic activity of palladium complexes
Single-component and environmentally stable palladium acetylides with the structures of PdL2(C equivalent to CR)(2) (L = PPh3, PBu3; R = p-C6H4C equivalent to CH. C6H5, H, CH2OH, CH2OCOCH3, CH2OCOC6H5, CH2OCOC6H4OH-o) are novel efficient initiating systems forp-diethynylbenzene polymerization. The polymerization proceeds under mild conditions to give soluble rr-conjugated polymers with molecular weights as high as 1.8 x 10(4) in yields as high as 84%. The catalytic property of these acetylides is related to phosphine and alkynyl ligands bonded to the metal atoms. Palladium complexes containing PPh3 ligand are much more active than that containing PBu3 ligand. The complexes containing polar alkynyl ligands show higher catalytic activity than the corresponding complexes containing non-polar ligands. For the complexes containing non-polar alkynyl ligands, the greater the conjugation degree of the alkynyl ligand, the higher the catalytic activity of the corresponding complex. For the complexes containing polar alkynyl ligands, the complexes containing ester ligands show higher catalytic activity than the corresponding complex containing alcohol ligand, and the catalytic activity of the complexes containing ester ligands increases with increasing acidity of the corresponding acids.