Metal Complexes in the Synthesis of Biodegradable Polymers: Achievements and Prospects

Mankaev, Badma N.; Karlov, Sergey S.

doi:10.3390/ma16206682

Cited by 16 publications

(2 citation statements)

References 192 publications

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“…In industry, biodegradable polymers are synthesized by ring-opening polymerization (ROP) of L -LA and other cyclic esters, catalyzed by metal complexes . It should be noted that effective catalytic systems have already been developed for the synthesis of poly( L -LA) and PLGA; however, selection or creating the initiator for the synthesis of copolymers is a different and at times challenging task …”

Section: Introductionmentioning

confidence: 99%

Diamidoamine Aluminum Complex as Effective Initiator for Random Copolymerization of Substituted Carbonate with L-Lactide

Agaeva,

Filippenko,

Mankaev

et al. 2024

Organometallics

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Designing a catalyst for random copolymerization by ring-opening polymerization (ROP) is an actual task. In the present work, we report the synthesis of aluminum complexes (R′ = Et, R′′ = Ph (5); R′ = Bn, R′′ = Ph (6); R′ = t-Bu, R′′ = Ph (7); R′ = R′′ = Ph (8)] based on diamidoamine pro-ligands. The reactivity of complexes in the ROP of ε-caprolactone (ε-CL) was studied. The highest activity was shown by complexes 5 and 8, containing phenyl groups at the terminal nitrogen atoms of the ligand in the ROP of ε-CL. Also, complex 5 was an effective initiator of copolymerization of 2-(benzyloxycarbonyl)-2-methyltrimethylene carbonate (TMC R ) and L-lactide (L-LA) which led to the formation of a random copolymer.

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Section: Introductionmentioning

confidence: 99%

Diamidoamine Aluminum Complex as Effective Initiator for Random Copolymerization of Substituted Carbonate with L-Lactide

Agaeva,

Filippenko,

Mankaev

et al. 2024

Organometallics

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“…Polylactide (PLA) and poly( ε -caprolactone) (PCL) have received a lot of attention over the last few years due to their biodegradability and attractive physical and mechanical properties [ 1 , 2 , 3 ]. The microstructures, physical-chemical properties, possible applications, and synthesis methods of these polymeric materials have been discussed in detail in a number of review papers, for example, [ 4 , 5 , 6 , 7 , 8 , 9 , 10 , 11 , 12 , 13 , 14 , 15 , 16 , 17 , 18 , 19 , 20 , 21 , 22 , 23 , 24 ]. The common method for the synthesis of PLA and PCL is the ring-opening polymerization (ROP) of corresponding monomers, e.g., ε -caprolactone ( ε -CL) and lactide (LA) monomers, with the use of structurally well-defined metal complexes that contain an initiating nucleophile, most commonly the alkoxy group OR, and a variety of ancillary ligands [ 2 , 5 , 25 , 26 ].…”

Section: Introductionmentioning

confidence: 99%

Titanium and Vanadium Complexes of Tridentate Phenoxy-Imine and Phenoxy-Amine Ligands and Their Application in the Ring-Opening Polymerization of Cyclic Esters

Białek,

Klimasińska,

Spaleniak

et al. 2023

Molecules

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Phenoxy-imine and phenoxy-amine proligands, with the additional OH donor groups 2,4-tBu2-6-(2-CH2(OH)-C6H4N=CH)C6H3OH (L1H2), 6-(2-CH2(OH)-C6H4N=CH)C6H3OH (L2H2), and 2,4-tBu2-6-(2-CH2(OH)-C6H4NH-CH)C6H3OH (L3H2), were synthesized and their titanium (Ti-L1–Ti-L3) and vanadium (V-L1–V-L2) complexes were prepared in reactions with Ti(OiPr)4 and VO(OiPr)3, respectively. All new compounds were characterized with the use of FTIR, 1H, and 13C NMR spectroscopy; X-ray crystallography was also used to study proligands. All the complexes proved to be active catalysts in the ring-opening polymerization (ROP) of ε-caprolactone, rac-lactide, and L-lactide in the melt. The effects of the complex structure (transition metal type, presence of tBu substituents, and type of nitrogen donor group), as well as the polymerization time and temperature, on the monomer conversion and polymer properties were investigated in detail.

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Synthesis of Aluminum Complexes Based on 2,6‐Bis(2‐hydroxyphenyl)Pyridines: Efficient Initiators for Ring‐Opening Polymerization of Cyclic Esters

Serova,

Lykov,

Mankaev

et al. 2024

ChemistrySelect

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The search for new initiators based on nontoxic metal complexes, allowing for the controlled production of polycaprolactone (PCL) and polylactide (PLA) is an actual task. In the present work, we report the synthesis of aluminum complexes 6a and 6b based on substituted 2,6‐bis(2‐hydroxyphenyl)pyridine pro‐ligands. The compositions and structures of the novel compounds were established by elemental analysis and 1H, 13C, NMR spectroscopy in the solid state by X‐ray diffraction analysis (6a and 6b). All the synthesized aluminum complexes are monomeric. Complexes 6a and 6b (in presence of benzyl alcohol (BnOH)) turned out to be active in the ring opening polymerization (ROP) of ε‐caprolactone (ε‐CL), L‐, rac‐lactide (L‐, rac‐LA) gave PCL and PLA with high molecular weights. The mechanism of the polymerization reaction for compounds С, 6a, and 6b was also investigated using the density functional theory (DFT) method. The substituent effect analyzed in terms of percent buried volume and non‐covalent interactions. The values of calculated Gibbs free activation energies correspond to the trend found experimentally.

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Metal Complexes in the Synthesis of Biodegradable Polymers: Achievements and Prospects

Cited by 16 publications

References 192 publications

Diamidoamine Aluminum Complex as Effective Initiator for Random Copolymerization of Substituted Carbonate with L-Lactide

Diamidoamine Aluminum Complex as Effective Initiator for Random Copolymerization of Substituted Carbonate with L-Lactide

Titanium and Vanadium Complexes of Tridentate Phenoxy-Imine and Phenoxy-Amine Ligands and Their Application in the Ring-Opening Polymerization of Cyclic Esters

Synthesis of Aluminum Complexes Based on 2,6‐Bis(2‐hydroxyphenyl)Pyridines: Efficient Initiators for Ring‐Opening Polymerization of Cyclic Esters

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