Synthesis of Unzipping Polyester and a Study of its Photochemistry

Joo, Wontae; Wang, Wade; Mesch, Ryan A.; Matsuzawa, Kensuke; Liu, Di; Willson, C. Grant

doi:10.1021/jacs.9b06285

Cited by 16 publications

(20 citation statements)

References 55 publications

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“…The ideal transient material has good mechanical properties, is readily accessible from inexpensive feedstocks, is processable by conventional methods, and is easily tailored to respond to different and orthogonal triggering stimuli. Depolymerization reactions are typically triggered by light, 5 acid, 6 and specific ions, 7 stimuli that are ubiquitous in everyday use. Single electron transfer (SET) triggering of transient polymers presents an alternative route to tunable transient materials.…”

Section: ■ Introductionmentioning

confidence: 99%

Triggered Transience of Plastic Materials by a Single Electron Transfer Mechanism

et al. 2020

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Transient polymers rapidly and controllably depolymerize in response to a specific trigger, typically by a chain-end unzipping mechanism. Triggers, such as heat, light, and chemical stimuli, are generally dependent on the chemistry of the polymer backbone or end groups. Single electron transfer (SET), in contrast to other triggering mechanisms, is achievable by various means including chemical, electrochemical, and photochemical oxidation or reduction. Here, we identify SET and subsequent mesolytic cleavage as the major thermal triggering mechanism of cyclic poly(phthalaldehyde) (cPPA) depolymerization. Multimodal SET triggering is demonstrated by both chemical and photoredox-triggered depolymerization of cPPA. Redox-active small molecules (p-chloranil and 1,3,5-trimethoxybenzene) were used to tune the depolymerization onset temperature of cPPA over the range 105−135 °C. Extending this mechanism to photoredox catalysis, N-methylacridinium hexafluorophosphate (NMAPF 6 ) was used to photochemically degrade cPPA in solution and thin films. Finally, we fabricated photodegradable cPPA monoliths with a storage modulus of 1.8 GPa and demonstrated complete depolymerization within 25 min of sunlight exposure. Sunlight-triggered depolymerization of cPPA is demonstrated and potentially useful for the manufacture of transient devices that vanish leaving little or no trace. Most importantly, this new mechanism is likely to inspire other SET-triggered transient polymers, whose development may address the ongoing crisis of plastic pollution.

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Section: ■ Introductionmentioning

confidence: 99%

Triggered Transience of Plastic Materials by a Single Electron Transfer Mechanism

et al. 2020

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“…Thus far, the most widely explored SIPs include polycarbamates, , poly(benzyl ether)s, polyphthalaldehydes, , and polyglyoxylates (PGs) . They have been explored for applications such as sensors, , transient electronics, − drug delivery vehicles, − and in recyclable plastics and composites. − In addition, new depolymerizable polymers including poly(benzyl ester)s, polycarboxypyrroles, and polyglyoxylamides continue to be developed to achieve different properties and meet the requirements for additional applications such as photolithography and kinetic hydrate inhibition in oil and gas lines …”

Section: Introductionmentioning

confidence: 99%

“…SIP backbones such as polycarbamates, , polycarbonates, , poly(benzyl ester)s, and polycarboxypyrroles have been synthesized by step-growth polymerization methods. These methods have allowed for the incorporation of many different pendent functional groups but typically result in relatively low degrees of polymerization (DP n ).…”

Section: Introductionmentioning

confidence: 99%

“…20 They have been explored for applications such as sensors, 15,21 transient electronics, 22−24 drug delivery vehicles, 25−27 and in recyclable plastics and composites. 28−30 In addition, new depolymerizable polymers including poly(benzyl ester)s, 31 polycarboxypyrroles, 32 and polyglyoxylamides 33 continue to be developed to achieve different properties and meet the requirements for additional applications such as photolithography 31 and kinetic hydrate inhibition in oil and gas lines. 34 SIP backbones such as polycarbamates, 15,16 polycarbonates, 35,36 poly(benzyl ester)s, 31 and polycarboxypyrroles 32 have been synthesized by step-growth polymerization methods.…”

Section: ■ Introductionmentioning

confidence: 99%

“…28−30 In addition, new depolymerizable polymers including poly(benzyl ester)s, 31 polycarboxypyrroles, 32 and polyglyoxylamides 33 continue to be developed to achieve different properties and meet the requirements for additional applications such as photolithography 31 and kinetic hydrate inhibition in oil and gas lines. 34 SIP backbones such as polycarbamates, 15,16 polycarbonates, 35,36 poly(benzyl ester)s, 31 and polycarboxypyrroles 32 have been synthesized by step-growth polymerization methods. These methods have allowed for the incorporation of many different pendent functional groups but typically result in relatively low degrees of polymerization (DP n ).…”

Section: ■ Introductionmentioning

confidence: 99%

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Transesterification of Poly(ethyl glyoxylate): A Route to Structurally Diverse Polyglyoxylates

et al. 2020

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Polyglyoxylates are a class of self-immolative polymers that depolymerize in solution and the solid state. The glyoxylic acid degradation product is a metabolite in the glyoxylate cycle and can also be processed in the liver in humans, making polyglyoxylates attractive for applications in the environment and in medicine. Although expanding the scope of available polyglyoxylates would enable new properties and applications, highly pure glyoxylate monomers are required for polymerization, and this level of purity is difficult to achieve for many potential monomers. To address this challenge, we report here the 1,5,7-triazabicyclo[4.4.0]dec-5-ene (TBD)-catalyzed post-polymerization transesterification of poly(ethyl glyoxylate) (PEtG) as a general method for the synthesis of directly inaccessible polyglyoxylates. Using a new end-capping strategy, PEtG compatible with the transesterification reaction was developed. n-Propanol, i-propanol, n-butanol, t-butanol, n-pentanol, n-hexanol, n-octanol, and benzyl alcohol were employed and the reactivities of these different alcohols were investigated. The resulting polyglyoxylates were characterized chemically and their thermal properties were compared. In all cases, the transesterified polyglyoxylates retained the stimuli-responsive depolymerization properties of the parent PEtG. In addition, functional polyglyoxylates based on allyl, propargyl, and furfuryl esters, which are suitable for subsequent click reactions, were prepared. The propargyl-functionalized polyglyoxylate was used to conjugate pyrene, and the resulting molecules underwent a change in fluorescence properties upon depolymerization.

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Rapid and Selective Photo‐degradation of Polymers: Design of an Alternating Copolymer with an o‐Nitrobenzyl Ether Pendant

Kubota

Ouchi

2023

Angewandte Chemie

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The development of polymers with on-demand degradability is required to alleviate the current global issues on polymer-waste pollution. Therefore, we designed a vinyl ether monomer with an o-nitrobenzyl (oNBn) group as a photo-deprotectable pendant (oNBnVE) and synthesized an alternating copolymer with an oNBn-capped acetal backbone via cationic copolymerization with p-tolualdehyde (pMeBzA). The resultant alternating copolymer could be rapidly degraded into lower-molecular-weight compounds upon simple exposure to UV irradiation without any reactants or catalysts, while it was sufficiently stable toward heat and ambient light. This degradation proceeds via cleavage of the hemiacetal structure generated upon photo-deprotection of the oNBn pendant. The oNBnpeculiar degradability allowed the exclusive photodegradation of the oNBnVE/pMeBzA segments in a diblock copolymer composed of oNBnVE/pMeBzA and benzyl vinyl ether (BnVE)/pMeBzA segments.

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Synthesis of Unzipping Polyester and a Study of its Photochemistry

Cited by 16 publications

References 55 publications

Triggered Transience of Plastic Materials by a Single Electron Transfer Mechanism

Triggered Transience of Plastic Materials by a Single Electron Transfer Mechanism

Transesterification of Poly(ethyl glyoxylate): A Route to Structurally Diverse Polyglyoxylates

Rapid and Selective Photo‐degradation of Polymers: Design of an Alternating Copolymer with an o‐Nitrobenzyl Ether Pendant

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