Systematic Study of Polyglyoxylamides as Powerful, High-Cloud-Point Kinetic Hydrate Inhibitors

Ree, Lilian H. S.; Sirianni, Quinton E. A.; Gillies, Elizabeth R.; Kelland, Malcolm A.

doi:10.1021/acs.energyfuels.8b04335

Cited by 21 publications

(31 citation statements)

References 42 publications

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“…PEtG has been synthesized to incorporate different end-caps that are responsive to light, heat, thiols, and hydrogen peroxide . Furthermore, the pendent ethyl ester groups on PEtG can be replaced with other alcohols to give different PGs or with amines to give polyglyoxylamides (PGAms), allowing their properties to be readily tuned. − However, the development of PGs that depolymerize rapidly and selectively in response to mildly acidic aqueous conditions (e.g., pH 5–6) has been a significant ongoing challenge. This challenge arises partly from the fact that pH-responsive end-caps such as trityl (Trit) and 4-monomethoxytrityl (MMT) exhibit only modest dependence on pH between pH 5 and 7.4.…”

Section: Introductionmentioning

confidence: 99%

Polyglyoxylamides with a pH-Mediated Solubility and Depolymerization Switch

et al. 2021

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Self-immolative polymers (SIPs) are characterized by their ability to depolymerize in response to the cleavage of a single end-cap or backbone moiety, making them attractive for numerous applications including sensors, transient plastics, and delivery vehicles. For many applications, it would be desirable to have an SIP capable of depolymerizing selectively under mildly acidic aqueous conditions. However, the poor solubility of most SIPs in water, accompanied by the competing effects of end-cap cleavage and depolymerization mechanisms, has made this a challenge. Here, we describe the development of polyglyoxylamides (PGAms) with pendent amino groups to achieve solubility switching at mildly acidic pH, which allows access of water to the end-cap and consequently depolymerization. PGAms with varying amino groups were synthesized from trityl end-capped poly(ethyl glyoxylate) (PEtG). While water-insoluble PEtG underwent no detectable depolymerization between pH 5 and 7.4 and water-soluble PGAms underwent rapid depolymerization regardless of pH in this range, a PGAm with N,N-diisopropylaminoethyl (DPAE) pendent groups underwent more rapid depolymerization at pH 5−6 compared to pH 7.4. PGAms were also incorporated into block copolymers with poly(ethylene glycol) (PEG). Nanoassemblies formed from PEG-PGAm(DPAE), swelled, disassembled, and depolymerized as the pH was lowered from 8 to 5. Copolymers lacking a solubility switch did not undergo pH-dependent disassembly or depolymerization. Overall, this work provides a new platform approach for the development of pH-sensitive SIP materials for a wide range of applications.

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Section: Introductionmentioning

confidence: 99%

Polyglyoxylamides with a pH-Mediated Solubility and Depolymerization Switch

et al. 2021

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“…Some PGAMs (PGAMa,f,g) were soluble in water, opening opportunities for applications requiring water solubility. For example, in collaboration with Ree and Kelland, we reported the study of PGAMs as kinetic hydrate inhibitors for the prevention of gas hydrate plugging in oil and gas lines . Overall, there are many potential applications of PGAMs that remain unexplored.…”

Section: Reversible Sipsmentioning

confidence: 99%

“…For example, in collaboration with Ree and Kelland, we reported the study of PGAMs as kinetic hydrate inhibitors for the prevention of gas hydrate plugging in oil and gas lines. 101 Overall, there are many potential applications of PGAMs that remain unexplored. However, the limited availability of end-caps that are stable to the amidation reaction, yet undergo stimuli-selective cleavage, is an ongoing challenge that must be addressed to fully exploit the PGAMs.…”

Section: ■ Reversible Sipsmentioning

confidence: 99%

Triggering Depolymerization: Progress and Opportunities for Self-Immolative Polymers

Yardley

Kenaree

Gillies³

2019

Macromolecules

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115

133

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Polymers that depolymerize end-to-end upon cleavage of their backbones or end-caps, often termed “self-immolative” polymers (SIPs), have garnered significant interest in recent years. They can be distinguished from other degradable and stimuli-responsive polymers by their ability to provide amplified responses to stimuli, as a single bond cleavage event is translated into the release of many small molecules through a cascade of reactions. Here, the synthesis and properties of the major classes of SIPs including poly(benzyl carbamate)s, poly(benzyl carbonate)s, poly(benzyl ether)s polyphthalaldehydes, polyglyoxylates, polyglyoxylamides, and poly(olefin sulfone)s are presented. In addition, their advantages and limitations as well as their recent applications in areas including sensors, drug delivery, micro- and nanopatterning, transient devices and composites, coatings, antibacterial, and recyclable plastics are described. Finally, the challenges associated with the development of new SIP backbones and their translation into commercial products are discussed.

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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%

“…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%

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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Systematic Study of Polyglyoxylamides as Powerful, High-Cloud-Point Kinetic Hydrate Inhibitors

Cited by 21 publications

References 42 publications

Polyglyoxylamides with a pH-Mediated Solubility and Depolymerization Switch

Polyglyoxylamides with a pH-Mediated Solubility and Depolymerization Switch

Triggering Depolymerization: Progress and Opportunities for Self-Immolative Polymers

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

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