Taking the Next Step—Model‐Based Analysis of Robust and Non‐Toxic Zn Catalysts for the Ring Opening Polymerization of Lactide in the Polymer Melt

Conen, Niclas; Fuchs, Martin; Hoffmann, Alexander; Herres‐Pawlis, Sonja; Jupke, Andreas

doi:10.1002/adsu.202200359

Cited by 5 publications

(5 citation statements)

References 66 publications

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“…Herein, the occurring decrease in catalytic activity was found to be caused by chain initiation by the ligand. Over the course of the polymerization time, this leads to an overall decreased catalytic activity [28] . However, the reached lactide conversion further indicates the applicability of the catalyst under industrial conditions.…”

Section: Resultsmentioning

confidence: 99%

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A Multitool for Circular Economy: Fast Ring‐Opening Polymerization and Chemical Recycling of (Bio)polyesters Using a Single Aliphatic Guanidine Carboxy Zinc Catalyst

et al. 2023

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A new aliphatic hybrid guanidine N,O‐donor ligand (TMGeech) and its zinc chloride complex ([ZnCl2(TMGeech)]) are presented. This complex displays high catalytic activity for the ring‐opening polymerization (ROP) of lactide in toluene, exceeding the toxic industry standard tin octanoate by a factor of 10. The high catalytic activity of [ZnCl2(TMGeech)] is further demonstrated under industrially preferred melt conditions, reaching high lactide conversions within seconds. To bridge the gap towards a sustainable circular (bio)economy, the catalytic activity of [ZnCl2(TMGeech)] for the chemical recycling of polylactide (PLA) by alcoholysis in THF is investigated. Fast production of different value‐added lactates at mild temperatures is demonstrated. Selective PLA degradation from mixtures with polyethylene terephthalate (PET) and a polymer blend, catalyst recycling, and a detailed kinetic analysis are presented. For the first time, chemical recycling of post‐consumer PET producing different value‐added materials is demonstrated using a guanidine‐based zinc catalyst. Therefore, [ZnCl2(TMGeech)] is a promising, highly active multitool, not only to implement a circular (bio)plastics economy, but also to tackle today's ongoing plastics pollution.

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Section: Resultsmentioning

confidence: 99%

“…Over the course of the polymerization time, this leads to an overall decreased catalytic activity. [28] However, the reached lactide conversion further indicates the applicability of the catalyst under industrial conditions.…”

Section: Ring-opening Polymerization Of Lactidementioning

confidence: 97%

A Multitool for Circular Economy: Fast Ring‐Opening Polymerization and Chemical Recycling of (Bio)polyesters Using a Single Aliphatic Guanidine Carboxy Zinc Catalyst

et al. 2023

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Section: Resultsmentioning

confidence: 99%

“…These observations are also in accordance with a former study on a zinc N,O hybrid guanidine complex. 53 Analogous to C3 , an experiment with the addition of 1 equivalent of FeCl 2 was conducted ([M]/[I]/[FeCl 2 ] = 2000 : 1 : 1, see Fig. 6 and Table 4 entry 11).…”

Section: Resultsmentioning

confidence: 99%

“…This decrease of k app during the polymerization process was also observed before for the zinc TMGasme systems and was attributed to the guanidine ligand functioning as an initiator for new growing polymer chains. 53 The iron(II) N,N hybrid guanidine complex C6 combines a high polymerization activity with stability. The experiments performed at an [M]/[I] ratio of 1000 : 1 lead to high conversions and no deactivation behavior was observed for this catalyst.…”

Section: Catalysis Science and Technology Papermentioning

confidence: 99%

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Understanding structure–activity relationships: iron(ii) complexes of “Legacy Guanidines” as catalysts for the synthesis of polylactide

Conrads,

Burkart,

Soerensen

et al. 2023

Catal. Sci. Technol.

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Syntheses of Cyclic Poly(l‐lactide)s by Means of Zinc‐Based Ring‐Opening Polymerization with Simultaneous Polycondensation (ROPPOC) Catalysts

Kricheldorf

Scheliga

Weidner

2023

Macro Chemistry & Physics

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Ring‐opening polymerizations of l‐lactide are studied in bulk at 140 or 160 °C with zinc n‐hexanoate, zinc 4‐chlorothiophenolate, and zinc pentafluoro thiophenolate (ZnSPF) as catalysts. The reactivity increases in the given order. With all three catalysts a high fraction of cycles is obtained only at polymerization (annealing) times around 7 d. With ZnSPF weight average molecular weights (Mw) up to 178 000, a Tm around 199 °C and a ΔHm around 99 J g−1 w ere achieved. The samples annealed for 4 or 7 d also display a saw tooth pattern of the mass peak distribution in the matrix‐assisted laser desorption/ionization time of flight spectra indicating transesterification reactions across the surface of extended ring crystals. This process optimizes the thermodynamical properties of the crystalline cyclic polylactides and is responsible for the high Tm and ΔHm values.

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Taking the Next Step—Model‐Based Analysis of Robust and Non‐Toxic Zn Catalysts for the Ring Opening Polymerization of Lactide in the Polymer Melt

Abstract: Figure 4. Representation of the molecular structures of the species involved in the ROP and included in the model.

Cited by 5 publications

References 66 publications

A Multitool for Circular Economy: Fast Ring‐Opening Polymerization and Chemical Recycling of (Bio)polyesters Using a Single Aliphatic Guanidine Carboxy Zinc Catalyst

A Multitool for Circular Economy: Fast Ring‐Opening Polymerization and Chemical Recycling of (Bio)polyesters Using a Single Aliphatic Guanidine Carboxy Zinc Catalyst

Understanding structure–activity relationships: iron(ii) complexes of “Legacy Guanidines” as catalysts for the synthesis of polylactide

Syntheses of Cyclic Poly(l‐lactide)s by Means of Zinc‐Based Ring‐Opening Polymerization with Simultaneous Polycondensation (ROPPOC) Catalysts

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