摘要
A series of Al complexes containing phenoxyimine ligands of the types R(1)(R(2))Al[O-2'-Bu-6-{(C(6)F(5))N=CH}C(6)H(3)] [R(1), R(2) = Me, Me (1a); Et, Et (1b); Me, Cl (1c)] and Me(2)Al[O-2-'Bu-6(ArN=CH)C(6)H(3)] [Ar = 2,6-F(2)C(6)H(3) (2a), 2,4-F(2)C(6)H(3) (3a), 3,4-F(2)C(6)H(3) (4a)] have been prepared and identified on the basis of NMR spectra and elemental analyses. Their structures were determined by X-ray crystallography, and these complexes fold a distorted tetrahedral geometry around Al. The ring-opening polymerizations (ROPs) of E-caprolactone (CL) using la-c in the presence,of PhCH(2)OH proceeded efficiently in a living manner, and the propagation rates were somewhat influenced by the anionic donor ligand employed (Me, Et, or Cl). The catalytic activity by 1a-6a [Ar = C(6)H(5) (5a), 2,6-Me(2)C(6)H(3) (6a)]-PhCH(2)OH catalyst systems was strongly affected by the aromatic substituent (Ar) in the imino group, and placement of fluorine substituents especially in the ortho-position strongly affected the catalytic activity. The ROPs by 2a-6a were accompanied by a certain degree of side reactions (transesterification), whereas the living polymerization systems can be accomplished using the C(6)F(5) analogues (1a-c). Therefore, the C6F5 substituent in the imino group plays an essential key role in the ROP of CL in terms of both the catalytic activity and maintaining a living manner.
- 出版日期2009-4-13