Controllable bulk solvent-free melt ring-opening polymerization (ROP) of l-lactide catalyzed by Ni(II) and Ni(II)–Ln(III) complexes based on the Salen-type Schiff-base ligand

• Published in: Journal of molecular catalysis. A, Chemical Chemical, 2011-03, Vol.337 (1), p.25-32
• Main Authors: Jin, Wen-Juan, Ding, Li-Qin, Chu, Zeng, Chen, Lei-Lei, Lü, Xing-Qiang, Zheng, Xiao-Yan, Song, Ji-Rong, Fan, Dai-Di
• Format: Article
• Language: English
• Subjects: Applied sciences; Bulk solvent-free melt ring-opening polymerization; Catalysis; Catalysts: preparations and properties; Chemistry; Exact sciences and technology; General and physical chemistry; l-Lactide; Organic polymers; Physicochemistry of polymers; Polymerization; Preparation, kinetics, thermodynamics, mechanism and catalysts; Salen-type Schiff base transition metal or mixed metal complex; Theory of reactions, general kinetics. Catalysis. Nomenclature, chemical documentation, computer chemistry
• ISSN: 1381-1169; 1873-314X
• DOI: 10.1016/j.molcata.2011.01.009

A monometallic (Ni 2+, 1) and a series of bimetallic (Ni 2+–Ln 3+, 2– 8) Salen-type Schiff-base complexes with different active species, could efficiently catalyze the bulk solvent-free melt ring-opening polymerization (ROP) of L-lactide, and the type of rare ions was important and influential factor contributing to the catalytic behavior. [Display omitted] ► d or d–f complexes based on Salen-type Schiff-base ligand. ► Controllable bulk solvent-free melt ring-opening polymerization (ROP) of l-lactide. ► Lewis acidity of active species (d or d–f) being relative to the catalytic activity. ► Intramolecular Ni⋯Ln separations being relative to the catalysis. A monometallic (Ni 2+, 1) and a series of bimetallic (Ni 2+–Ln 3+, Ln = Ce ( 2); Ln = Nd ( 3); Ln = Sm ( 4); Ln = Eu ( 5); Ln = Tb ( 6); Ln = Ho ( 7); Ln = Tm ( 8)) complexes based on the Salen-type Schiff-base ligand H 2 L ( H 2 L = N,N′-bis(3-methoxysalicylidene)ethylene-1,2-diamine) were synthesized and characterized by EA, FT-IR, ESI-MS and X-ray crystallography. The catalysis results showed that the two kinds of complexes with different active species, could efficiently catalyze the bulk solvent-free melt ring-opening polymerization (ROP) of l-lactide with moderate molecular weights and narrow molecular weight distributions. Especially for the series of bimetallic complexes 2– 8, the involvement of rare ions effectively passivated the catalytic behaviors on the ROP of l-lactide, while was in favor of the increase of polymeric molecular weights ( M w or M n) and the polymerization controllability, and the type of rare ions was important and influential factor contributing to the catalytic behaviors.