Selective or living organopolymerization of a six-five bicyclic lactone to produce fully recyclable polyesters

Cywar, Robin M.; Zhu, Jian‐Bo; Chen, Eugene Y.‐X.

doi:10.1039/c9py00190e

Cited by 51 publications

(38 citation statements)

References 43 publications

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“…The same group recently presented the organocatalytic ROP of similar six-five bicyclic lactone (4, to produce high molecular weight recyclable polyesters utilizing organobase/ (thio)urea binary catalysts. 19 Despite the success achieved in recyclable polymers over the past several years, fully recyclable polymeric materials are still limited, especially those with functional groups. Lu et al 20 recently developed recyclable polythioesters from biomass-sourced bridged bicyclic thiolactones with side chain allyl functional groups, which can be further modified and provide opportunities to adjust the polythioesters' properties.…”

Section: Introductionmentioning

confidence: 99%

Chemoselective Polymerization of Fully Biorenewable α-Methylene-γ-Butyrolactone Using Organophosphazene/Urea Binary Catalysts Toward Sustainable Polyesters

Shen

Xiong

et al. 2021

CCS Chem

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Despite the great potential of biorenewable α-methylene-γ-butyrolactone (MBL) to produce functional, recyclable polyester, the ring-opening polymerization (ROP) of MBL remains a challenge due to the competing polymerization of the highly reactive exocyclic double bond and low-strained five-membered ring. In this contribution, we present the first organocatalytic chemoselective ROP of MBL to exclusively produce functional unsaturated polyester by utilizing a phosphazene base/urea binary catalyst. We show that delicate chemoselectivity can be realized by controlling the temperature and using selected urea catalysts. The obtained polyester can be completely recycled back to its monomer by chemolysis under mild conditions. Experimental and theoretical calculations provide mechanistic insights and indicate that the ROP pathway is kinetically favored by using urea with stronger acidity at low temperatures.

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Section: Introductionmentioning

confidence: 99%

Chemoselective Polymerization of Fully Biorenewable α-Methylene-γ-Butyrolactone Using Organophosphazene/Urea Binary Catalysts Toward Sustainable Polyesters

Shen

Xiong

et al. 2021

CCS Chem

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“…[61][62][63][64][65][66][67] Such a method has been applied to the ROP of lactones, and LA to prepare cyclic polyesters. [68][69][70] Recently, Yang's group 71 demonstrated that a Lewis-pair catalytic system, a primary amine (1-hexyl-NH 2 ) as a Lewis base and Zn(C 6 F 5 ) 2 as a Lewis acid (Scheme 3b), could mediate the controlled ROP of OCAs. Note that such a Lewis pair has been applied for ROPs of LA and ε-caprolactone.…”

Section: Metal Catalysts For O-carboxyanhydride Polymerizationmentioning

confidence: 99%

Controlled Ring-Opening Polymerization of O-Carboxyanhydrides to Synthesize Functionalized Poly(α-Hydroxy Acids)

2021

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Poly(α-hydroxy acids), as a family of biodegradable polyesters, are valuable materials due to their broad applications in packaging, agriculture, and biomedical engineering. Herein we highlight and explore recent advances of catalysts in controlled ring-opening polymerization of O-carboxyanhydrides towards functionalized poly(α-hydroxy acids), especially metal catalyst-mediated controlled polymerization. Limitations of current polymerization strategies of O-carboxyanhydrides are discussed.

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“…Only oligomers were produced with a maximum value of 20% of monomer conversion [72,73]. The polymerization of αOHγBL was carried out at 90 °C using TfOH, producing oligomers with dehydration [56].…”

Section: Brønsted Acid-catalyzed Rop/rocp Of γ-Lactonesmentioning

confidence: 99%

“…Fluorosulfonic acid (FSO3H), TfOMe and TfOH were quite helpful to copolymerize γBL (or (R)-γVL) with different comonomers such as glycolide, 3,4-trans cyclohexylring-fused γBL (3,4-T6L) or βBL, allowing up to 30% of γBL incorporation into low molar mass copolyester chains [62][63][64][65]73]. Phosphoric acid (H3PO4) could also achieve the copolymerization of γBL, γVL or γCL with εCL in bulk at 200 °C [74].…”

Section: Brønsted Acid-catalyzed Rop/rocp Of γ-Lactonesmentioning

confidence: 99%

“…Two different polymerization mechanisms were proposed, depending on the presence of an alcohol as the initiator or not. In absence of an alcohol, γBL can be directly deprotonated by the superbase to produce a reactive enolate species.This results in a mixture of linear PγBL with acylated lactone/H chain ends (PγBLL1) and cyclic PγBL (PγBLC), the latter was believed to be achieved by a back- and NHO3 [24] (up to down, respectively), (b) ROP of 4,5-T6L by NHCs [73].…”

Section: Organic Base-catalyzed Rop/rocp Of γ-Lactonesmentioning

confidence: 99%

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Ring-opening polymerization of γ-lactones and copolymerization with other cyclic monomers

Song

Pascouau

Zhao

et al. 2020

Progress in Polymer Science

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Triggered by raised environmental awareness and the rising requirements for sustainable polymers such as degradable or recyclable polymers, studies on ring-opening (co)polymerization (ROP/ROCP) of (bio-based) cyclic monomers (e.g., cyclic esters, lactides, epoxides etc.) have been booming in recent years. Renewable five-membered γ-butyrolactone (γBL) and derivatives would thus be a desirable feedstock to produce poly(γ-butyrolactone) (PγBL) and different (bio-based) functional polyesters. Their copolymerization with other cyclic monomers could also afford an alternative to tune the properties of the resulting materials.Although γBL was traditionally regarded "non-polymerizable", some progresses were made recently concerning the ROP/ROCP of γBL and derivatives. More importantly, some polyesters could be totally depolymerized back to their monomers by thermal or chemical treatment. This review is specially focused on ROP of γ-lactones and their copolymerization with other cyclic monomers by different catalytic/initiating systems, including Lewis/Brønsted acids, organic bases and alkali metal compounds, organometallic compounds, and cooperative bicomponent catalytic systems. The depolymerization process of some obtained polyesters is also discussed.

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Selective or living organopolymerization of a six-five bicyclic lactone to produce fully recyclable polyesters

Cited by 51 publications

References 43 publications

Chemoselective Polymerization of Fully Biorenewable α-Methylene-γ-Butyrolactone Using Organophosphazene/Urea Binary Catalysts Toward Sustainable Polyesters

Chemoselective Polymerization of Fully Biorenewable α-Methylene-γ-Butyrolactone Using Organophosphazene/Urea Binary Catalysts Toward Sustainable Polyesters

Controlled Ring-Opening Polymerization of O-Carboxyanhydrides to Synthesize Functionalized Poly(α-Hydroxy Acids)

Ring-opening polymerization of γ-lactones and copolymerization with other cyclic monomers

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