Functionalizable and Chemically Recyclable Thermoplastics from Chemoselective Ring‐Opening Polymerization of Bio‐renewable Bifunctional α‐Methylene‐δ‐valerolactone

Li, Jiandong; Liu, Fusheng; Liu, Yalei; Shen, Yong; Li, Zhibo

doi:10.1002/ange.202207105

Cited by 10 publications

(6 citation statements)

References 45 publications

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“…The chemoselective controlled ROP of MVL to produce exclusive functionalizable polyester (PMVL ROP ) was recently reported (Figure ). In comparison to the ROP of MBL, MVL with the more strained six-membered lactone showed a larger polymerizability and a moderate T c (Table , run 13). In the presence of strong base/urea as the binary catalyst at RT, MVL can undergo controlled ROP to prepare PMVL ROP with a high M n value of 74.6 kDa.…”

Section: Closed-loop Recyclable Polyestersmentioning

confidence: 99%

Ring-Opening Polymerization of Lactones to Prepare Closed-Loop Recyclable Polyesters

Li,

Shen,

2024

Macromolecules

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The large production and indiscriminate disposal of plastics have resulted in serious resource and global environmental crises, which has raised a demand to develop a more sustainable and circular plastics economy. An ideal strategy to address the end-of-life issue of plastics is to develop nextgeneration polymers with closed-loop life cycles, which can be selectively depolymerized back to monomers at the end of their service life. Aliphatic polyesters prepared by ring-opening polymerization (ROP) of moderately strained lactones have shown great potential in closed-loop recyclable polymers. This Perspective highlights the recent achievements for closed-loop recyclable polyesters that are derived from four-, five-, six-, and seven-membered lactones by focusing on the discussion of thermodynamic and kinetic considerations, monomer design principles and polymer preparations, material properties, and chemical recyclability. Finally, the current challenges and possible directions for closed-loop recyclable polymers are also discussed.

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Section: Closed-loop Recyclable Polyestersmentioning

confidence: 99%

Ring-Opening Polymerization of Lactones to Prepare Closed-Loop Recyclable Polyesters

Li,

Shen,

2024

Macromolecules

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“…Similarly, for the homopolymers derived from five-or six-membered lactone monomers (MVL vs VL, M γ BL vs γBL), the incorporation of the α-methylene group made T g of the polymer increase. 24,28,31 The thermal properties of PMDXO1 are significantly dependent on its thermal history. After the first heating to 280 °C and cooling to −70 °C with a rate of 10 °C/min, the sample was heated again.…”

Section: Rop Of Mdxomentioning

confidence: 99%

“…The ROP conditions have to be carefully optimized to avoid the plausible competing VAP. 24,28,30,31 Copolymerization of MDXO with CL or DXO. Copolymerization is an effective approach to tune the properties of aliphatic polyesters.…”

Section: Rop Of Mdxomentioning

confidence: 99%

Synthesis and Post-Functionalization of Poly(conjugated ester)s Based on 3-Methylene-1,5-dioxepan-2-one

Qian

Lai

et al. 2022

Biomacromolecules

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Poly(α-methylene ester)s are an attractive type of functional aliphatic polyesters that represent a platform for the fabrication of various biodegradable and biomedical polymers. Herein, we report the controlled ring-opening polymerization (ROP) of a seven-membered α-methylene lactone (3-methylene-1,5-dioxepan-2-one, MDXO) that was synthesized based on the Baylis–Hillman reaction. The chemoselective ROP of MDXO was catalyzed by diphenyl phosphate (DPP) at 60 °C or stannous octoate (Sn(Oct)2) at 130 °C, generating α-methylene-containing polyester (PMDXO) with a linear structure and easily tunable molar mass. The ring-opening copolymerization of MDXO with ε-caprolactone or 1,5-dioxepan-2-one was also performed under the catalysis of DPP or Sn(Oct)2 to afford copolymers with different compositions and sequence structures that are influenced by the kinds of monomers and catalysts. PMDXO is a slowly crystallizable polymer with a glass transition temperature of ca. −33 °C, and its melting temperature and enthalpy are significantly influenced by the thermal history. The thermal properties of the copolymers are dependent on their composition and sequence structure. Finally, the post-modification of PMDXO based on the thiol-Michael addition reaction was briefly explored using triethylamine as a catalyst. Given the optimized condition, PMDXO could be dually modified to afford biodegradable polyesters with different functionalities.

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“…The development of a circular polymer economy requires clever polymer designs that enable chemical recycling to monomer (CRM) or chemical recycling via upcycling methodologies. , In this research field, polymers synthesized by ring-opening polymerization (ROP) of heterocyclic monomers are of large interest due to the equilibrium nature of this type of polymerization, which provides an inherent recycling path via reverse ring-closing depolymerization (RcDP). , Some examples of monomers for which both ROP and RcDP have been demonstrated are lactide (LA), γ-butyrolactone, α-methylene-δ-valerolactone, 4,5- trans -hexahydro-2(3 H )-benzofuranone, , 3,4- trans -hexahydro-2(3 H )-benzofuranone, β-methyl-δ-valerolactone, δ-caprolactone, , and different trimethylene carbonate derivatives. − However, to meet the requirements of chemical recyclability while providing polymers with a wide range of different material properties, a larger library of recyclable monomers and recycling methodologies has to be developed. Moreover, the range of polymer properties can be broadened even further when these monomers are to be combined into different copolymer structures. − , …”

Section: Introductionmentioning

confidence: 99%

Design for Recycling: Polyester- and Polycarbonate-Based A–B–A Block Copolymers and Their Recyclability Back to Monomers

et al. 2023

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Chemical recycling to monomers (CRMs) of A–B–A block copolymers is governed by the chemical structure and thereby the thermodynamic behavior of different block constituents. Here, we show how a thermodynamic toolkit based on a cyclic monomer structure and solvent properties can be utilized in the design of recyclable A–B–A block copolymers with varying material properties. By combining four cyclic monomers lactide, ε-decalactone, 2,2-diethyltrimethylene carbonate, and trimethylene carbonate, three different block copolymers were created, suitable for different CRM scenarios. The chemical structure of the soft midblock (ε-decalactone or trimethylene carbonate) appeared to have a critical impact both on the ring-closing depolymerization behavior and mechanical properties, where changing from a polyester to a polycarbonate soft block increased Young’s modulus from 14 to 200 MPa. Hence, this work demonstrates the complexity as well as the opportunities in the design of macromolecular structures for a circular economy.

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Functionalizable and Chemically Recyclable Thermoplastics from Chemoselective Ring‐Opening Polymerization of Bio‐renewable Bifunctional α‐Methylene‐δ‐valerolactone

Cited by 10 publications

References 45 publications

Ring-Opening Polymerization of Lactones to Prepare Closed-Loop Recyclable Polyesters

Ring-Opening Polymerization of Lactones to Prepare Closed-Loop Recyclable Polyesters

Synthesis and Post-Functionalization of Poly(conjugated ester)s Based on 3-Methylene-1,5-dioxepan-2-one

Design for Recycling: Polyester- and Polycarbonate-Based A–B–A Block Copolymers and Their Recyclability Back to Monomers

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