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Synthesis and characterization of salen-Ti(IV) complex and application in the controllable polymerization of D, L-lactide.

ABSTRACT: Poly(lactic acid) has been extensively investigated in the biomedical field because of its good biocompatibility and biodegradability. As an important method of poly(lactic acid) synthesis, metal complex-catalyzed ring-opening polymerization (ROP) of lactide can achieve a controllable lactide polymerization through the selection of appropriate ligands and metals. In this study, a novel metal (LTi-O)2 complex was synthesized and structurally characterized. (LTi-O)2 showed a relatively high catalytic activity and controllability of Poly(D, L-lactide) (PDLLA) molecular weights (polydispersity index of 1.02-1.22) in the ROP of D,L-lactide. The kinetic equation of D,L-LA ROP catalyzed by (LTi-O)2 could be expressed as-d[M]/dt = k[M]2[(LTi-O)2]1, and the reaction activation energy was 95.67 kJ·mol-1. Physical/chemical properties and biocompatibility evaluation results showed that PDLLA obtained through the (LTi-O)2-catalyzed ROP of D,L- lactide exhibited a good degradation performance and excellent biocompatibility.

SUBMITTER: Li X

PROVIDER: S-EPMC6071980 | biostudies-literature |

REPOSITORIES: biostudies-literature

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Overcoming aggregation in indium salen catalysts for isoselective lactide polymerization.

Project description:A methodology for controlling aggregation in highly active and isoselective indium catalysts for the ring opening polymerization of racemic lactide is reported. A series of racemic and enantiopure dinuclear indium ethoxide complexes bearing salen ligands [(ONNOR)InOEt]2 (R = Br, Me, admantyl, cumyl, t-Bu) were synthesized and fully characterized. Mononuclear analogues (ONNOR)InOCH2Pyr (R = Br, t-Bu, SiPh3) were synthesized by controlling aggregation with the use of chelating 2-pyridinemethoxide functionality. The nuclearity of metal complexes was confirmed using PGSE NMR spectroscopy. Detailed kinetic studies show a clear initiation period for these dinuclear catalysts, which is lacking in their mononuclear analogues. The polymerization behavior of analogous dinuclear and mononuclear compounds is identical and consistent with a mononuclear propagating species. The isotacticity of the resulting polymers was investigated using direct integration and peak deconvolution methodologies and the two were compared.

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Study of ligand substituent effects on the rate and stereoselectivity of lactide polymerization using aluminum salen-type initiators.

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Undiscovered Potential: Ge Catalysts for Lactide Polymerization.

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Project description:Catalytic oxidative nitrene transfer from azides with the early transition metals is rare, and has not been observed without the support of redox noninnocent spectator ligands. Here, we report the formal [2+2+1] coupling of azides and alkynes via TiII/TiIV redox catalysis from simple Ti halide imido precatalysts. These reactions yield polysubstituted N-alkyl pyrroles, including N-benzyl protected pyrroles and rare examples of very electron rich pentaalkyl pyrroles. Mechanistic analysis reveals that [2+2+1] reactions with bulky azides have different mechanistic features from previously-reported reactions using azobenzene as a nitrene source.

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