Kinetic, thermal, structural and degradation studies on the effect of meta-substituted aromatic-aliphatic polyesters built through ring-opening polymerisation

Makwana, Vishalkumar A.; Larrañaga, Aitor; Vilas, José Luis; Lizundia, Erlantz

doi:10.1016/j.polymdegradstab.2019.108984

Cited by 8 publications

(7 citation statements)

References 34 publications

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“…In a study addressing the limited thermal stability of PDHB (T d,5% ≈ 180 °C), Lizundia and co-workers investigated the effects of substituents at the meta position of the benzene ring on the polymerization and depolymerization kinetics. 592 Utilizing the Al-1 catalyst, they observed that electronwithdrawing groups accelerated the degradation rates and enabled selective depolymerization back to cyclic monomers in just 10 min at 110 °C. Notably, polymers P(R-DHB) with R = Me, OMe, F, and Br exhibited improved thermal stabilities with T d,5% ranging between 230 and 260 °C.…”

Section: Chain-growth Ring-opening Polymerizationmentioning

confidence: 99%

Recyclable and (Bio)degradable Polyesters in a Circular Plastics Economy

Shi,

Quinn,

Diment

et al. 2024

Chem. Rev.

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Polyesters carrying polar main-chain ester linkages exhibit distinct material properties for diverse applications and thus play an important role in today's plastics economy. It is anticipated that they will play an even greater role in tomorrow's circular plastics economy that focuses on sustainability, thanks to the abundant availability of their biosourced building blocks and the presence of the main-chain ester bonds that can be chemically or biologically cleaved on demand by multiple methods and thus bring about more desired end-of-life plastic waste management options. Because of this potential and promise, there have been intense research activities directed at addressing recycling, upcycling or biodegradation of existing legacy polyesters, designing their biorenewable alternatives, and redesigning future polyesters with intrinsic chemical recyclability and tailored performance that can rival today's commodity plastics that are either petroleum based and/or hard to recycle. This review captures these exciting recent developments and outlines future challenges and opportunities. Case studies on the legacy polyesters, poly(lactic acid), poly(3-hydroxyalkanoate)s, poly(ethylene terephthalate), poly(butylene succinate), and poly(butylene-adipate terephthalate), are presented, and emerging chemically recyclable polyesters are comprehensively reviewed.

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Section: Chain-growth Ring-opening Polymerizationmentioning

confidence: 99%

Recyclable and (Bio)degradable Polyesters in a Circular Plastics Economy

Shi,

Quinn,

Diment

et al. 2024

Chem. Rev.

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“…[ 6,14,18‐23 ] There are two main modification methods including the introduction of heteroatoms in the CL ring and the incorporation of sided chains or fused rings. [ 14,19‐21,24 ] Representative monomers were summarized in Figure 1 such as 1,5‐dioxepan‐2‐ one (DXO), [ 22 ] 2,3‐dihydro‐5 H ‐1,4‐benzodioxepin‐5‐one (2,3‐DHB) and its derivatives, [ 25‐26 ] 1,4‐oxathiepan‐7‐one (OTO), [ 27 ] and benzo‐thia‐caprolactones (BOTO‐I, BOTO‐II, and BOTO‐III). [ 28 ] Recently, our group has developed a synthetic method to construct monomers 5,6‐T6GDXO and 5,6‐T6GOTO with fused‐rings, which underwent stereoselective living polymerization to afford aliphatic polyesters with well‐controlled molecular weights and high tacticity.…”

Section: Background and Originality Contentmentioning

confidence: 99%

Ring‐Opening Polymerization of a Benzyl‐Protected Cyclic Ester towards Functional Aliphatic Polyester^†

et al. 2022

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Comprehensive Summary Monomer design strategy has become a powerful tool to access polymers with desired and diverse functionalities. Here, we designed a novel monomer 2‐((benzyloxy)methyl)‐1,4‐oxathiepan‐7‐one (BTO) via installing a benzyl ether side chain to the structure of 1,4‐oxathiepan‐7‐one (OTO). The ring‐opening polymerization of BTO with Zn1 as the catalyst demonstrated the characteristics of living polymerization with turnover frequency (TOF) up to 2520 h−1. With a [BTO]0/[Zn1]0/[I]0 feed ratio of 2000/2/1, polymer with high number‐average molecular weight (Mn = 536 kDa) and narrow dispersity (Ð = 1.06) was obtained. The produced polymer with a glass transition temperature of ‐17°C behaved as an elastomer at room temperature. Consequently, the monomer BTO was copolymerized with L‐LA to modulate the mechanical properties of P(L‐LA). When the BTO content is 10%, the copolymer exhibits excellent strength (24 MPa) and elongation at break (270%), affording a crystalline, hard, and tough plastic material that combines the high ductility of P(BTO) and the high modulus of P(L‐LA). In addition, the oxidation of P(BTO) to P(BTO)‐SO2 led to an improvement of Tg from ‐17°C to 38°C. Debenzylation of P(BTO)‐SO2 afforded P(BTO)‐SO2‐OH containing free hydroxyl groups. Ultimately, P(BTO) could be hydrolyzed under a base condition to recover the corresponding hydroxyl acid intermediate, which could be used to prepare the monomer again and complete the closed‐loop from monomer to polymer to monomer.

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“…In a following work, Makwana, Lizundia and co-workers investigated the substituent effect on the meta -position of benzene ring, and revealed a resulting P(R-DHB) showing an improved thermal stability, specifically with a T d in the range of 230 to 260 °C. 62 In 2021, the Li research group designed three constitutional isomers of benzo-thia-caprolactones with great chemical recyclability to monomers under bulk thermal conditions. 63 The resulting semiaromatic polyesters displayed T d values ranging from 180 to 280 °C.…”

Section: Introductionmentioning

confidence: 99%

Leveraging the monomer structure for high-performance chemically recyclable semiaromatic polyesters

Fan

Xing

et al. 2023

Polym. Chem.

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Kinetic, thermal, structural and degradation studies on the effect of meta-substituted aromatic-aliphatic polyesters built through ring-opening polymerisation

Cited by 8 publications

References 34 publications

Recyclable and (Bio)degradable Polyesters in a Circular Plastics Economy

Recyclable and (Bio)degradable Polyesters in a Circular Plastics Economy

Ring‐Opening Polymerization of a Benzyl‐Protected Cyclic Ester towards Functional Aliphatic Polyester^†

Leveraging the monomer structure for high-performance chemically recyclable semiaromatic polyesters

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Kinetic, thermal, structural and degradation studies on the effect of meta-substituted aromatic-aliphatic polyesters built through ring-opening polymerisation

Cited by 8 publications

References 34 publications

Recyclable and (Bio)degradable Polyesters in a Circular Plastics Economy

Recyclable and (Bio)degradable Polyesters in a Circular Plastics Economy

Ring‐Opening Polymerization of a Benzyl‐Protected Cyclic Ester towards Functional Aliphatic Polyester†

Leveraging the monomer structure for high-performance chemically recyclable semiaromatic polyesters

Contact Info

Product

Resources

About

Ring‐Opening Polymerization of a Benzyl‐Protected Cyclic Ester towards Functional Aliphatic Polyester^†