Ultra-High-Molecular-Weight Poly(Dioxolane): Enhancing the Mechanical Performance of a Chemically Recyclable Polymer

Hester, H Grace; Abel, Brooks A.; Coates, Geoffrey W.

doi:10.1021/jacs.3c01901

Cited by 38 publications

(28 citation statements)

References 24 publications

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“…Selective chemical recycling of poly(1,3-dioxolane) into monomer with a near-quantitative yield was achieved with a strong acid catalyst (e.g., camphorsulfonic acid, CSA or diphenylphosphoric acid, DPP) at elevated temperatures of 100–150 °C (Figure c). Very recently, the same group further developed a metal-free, economically friendly polymerization system to synthesize ultrahigh-molecular-weight (UHMW) poly(1,3-dioxolane) with molar masses greater than 1000 kg/mol, which demonstrated similar tensile properties to UHMW polyethylene (Figure a,b) …”

Section: Recent Developments In Depolymerizable Backbonesmentioning

confidence: 99%

Emerging Trends in the Chemistry of End-to-End Depolymerization

Deng,

Gillies

2023

JACS Au

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Over the past couple of decades, polymers that depolymerize end-to-end upon cleavage of their backbone or activation of a terminal functional group, sometimes referred to as "self-immolative" polymers, have been attracting increasing attention. They are of growing interest in the context of enhancing polymer degradability but also in polymer recycling as they allow monomers to be regenerated in a controlled manner under mild conditions. Furthermore, they are highly promising for applications as smart materials due to their ability to provide an amplified response to a specific signal, as a single sensing event is translated into the generation of many small molecules through a cascade of reactions. From a chemistry perspective, end-to-end depolymerization relies on the principles of self-immolative linkers and polymer ceiling temperature (T c ). In this article, we will introduce the key chemical concepts and foundations of the field and then provide our perspective on recent exciting developments. For example, over the past few years, new depolymerizable backbones, including polyacetals, polydisulfides, polyesters, polythioesters, and polyalkenamers, have been developed, while modern approaches to depolymerize conventional backbones such as polymethacrylates have also been introduced. Progress has also been made on the topological evolution of depolymerizable systems, including the introduction of fully depolymerizable block copolymers, hyperbranched polymers, and polymer networks. Furthermore, precision sequence-defined oligomers have been synthesized and studied for data storage and encryption. Finally, our perspectives on future opportunities and challenges in the field will be discussed.

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Section: Recent Developments In Depolymerizable Backbonesmentioning

confidence: 99%

Emerging Trends in the Chemistry of End-to-End Depolymerization

Deng,

Gillies

2023

JACS Au

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“…For example, Coates and co-workers presented the reversible-deactivation cationic ROP of cyclic acetals to produce high-molecular-weight poly(1,3-dioxolane) (PDXL) with M n up to 220 kDa, which behaved as a tough thermoplastic with tensile strength comparable to some commodity polyolefins while remaining the capability of recycling back to monomer . Recently, they further improved the mechanical properties by accessing ultra-high-molecular-weight PDXL ( M n > 1000 kDa) with triethyl oxonium salts as initiators in the presence of a proton trap . Note that 1,3-dioxolane can be commercially prepared on a large scale from formaldehyde and ethylene glycol.…”

Section: Introductionmentioning

confidence: 99%

Rapid and Controlled Ring-Opening (Co)Polymerization of Bio-Sourced Alkyl-δ-Lactones To Produce Recyclable (Co)Polyesters and Their Application as Pressure-Sensitive Adhesives

et al. 2023

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It is attractive to develop chemically recyclable polymers with desirable performances from commercial monomers to avoid the expensive and time-consuming scalable process for completely new monomers. In this contribution, we present the rapid and controlled ring-opening polymerization (ROP) of bio-sourced commercial alkyl-δ-lactones to produce closed-loop recyclable polyesters in the presence of an organophosphazene base (tBu-P2)/urea binary catalyst. The obtained polyesters are capable of recycling back to pristine monomers by simply heating them in bulk in the presence of stannous octanoate (Sn(Oct)2) as the catalyst. The effects of alkyl substituent length on the polymerization kinetics, thermodynamics, as well as the properties of resultant poly(alkyl-δ-lactone)s were investigated. Well-defined triblock copolymers consisting of poly(alkyl-δ-lactone)s as soft middle block and PLLA as hard end block were successfully prepared by one-pot, sequential ROP of alkyl-δ-lactones and l-lactide (l-LA). These triblock copolymers can be used as pressure-sensitive adhesives without the addition of tackifiers or other additives. The chemical recycling of these triblock copolymers to recover ethyl lactate and alkyl-δ-lactones with high yields was achieved by alcoholysis and then distillation under reduced pressure.

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“…A variety of cyclic monomers have been utilized to access depolymerizable polymers, including lactones, 12,16 cyclic carbonates, 15,17–19 cyclic acetals, 14,20 and cycloalkenes. 9,11,13,21,22 Amongst all these types, cycloalkenes form polymers without heteroatoms along the backbone, providing greater resistance to hydrolytic degradation.…”

Section: Introductionmentioning

confidence: 99%