A molecular dynamics perspective on the cyclization efficiency for poly(2-oxazoline)s and poly(2-oxazine)s

Huettner, Nick; Dargaville, Tim R.; Gandhi, Neha S.

doi:10.1039/d3py00319a

Cited by 3 publications

(1 citation statement)

References 48 publications

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“…After building and optimizing the geometry of single chains within Avogadro 56 1.14*CM1A charges with OPLS-AA parameters were derived through PolyParGen. [57][58][59][60] While to our knowledge this class of polythioamides has not been simulated before, the chosen force field has been successfully used in recent works for poly(2-alkyl-2-oxazoline)s of the same length, 61 as well as for thioamide containing small molecules. 62 Chains were solvated with TIP3P water 63 in a cubic box with a minimum border-tosolute distance of 1 nm.…”

Section: Molecular Modelingmentioning

confidence: 99%

Thionation of poly(2-ethyl-2-oxazoline) and its effect on solubility and cloud point

Hacioglu,

Baddam,

Kerr

et al. 2024

Preprint

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Many water-soluble polymers undergo phase separation above their lower critical solution temperature (LCST) in aqueous solutions. Generally, the LCST is controlled via the polymer-solvent interactions, which in turn are highly structure dependent and typically tuned via the polymer side chain. For example, the LCST for the poly(2-oxazoline) family can be tuned via the length of the polymer side chain. In particular, the LCST of poly(2-ethyl-2-oxazoline) varies between 60-100 °C, depending on its molar mass, polymer architecture and concentration. Here, we introduce LCST adjustment via modification of the carbonyl of the amide moiety of poly(2-oxazoline)s. We introduce poly(2-ethyl-2-oxazoline-co-N-propiothioacetyl ethylene imine), synthesized from poly(2-ethyl-2-oxazoline) using Lawesson’s reagent. The degree of thionation of the polymers was varied and characterized using spectroscopic methods and elemental analysis. While the glass transition temperatures of the copolymers increase with increasing thionation degree, decomposition temperatures decrease. Interestingly, polymers with less than 20% thionation degree were soluble in water with LCST behavior. The cloud point temperatures decrease with increasing thionation degree, due to weaker hydrogen bonding ability of thioamides and decreased polarity.

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Section: Molecular Modelingmentioning

confidence: 99%

Thionation of poly(2-ethyl-2-oxazoline) and its effect on solubility and cloud point

Hacioglu,

Baddam,

Kerr

et al. 2024

Preprint

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Influence of polymer amphiphilicity on the cyclization efficiency of poly(2-oxazoline)s

Huettner,

Frisch,

Dargaville

2024

European Polymer Journal

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Thionation of Poly(2-ethyl-2-oxazoline) and Its Effect on Solubility and Cloud Point

Hacioglu,

Baddam,

Kerr

et al. 2024

Macromolecules

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Many water-soluble polymers undergo phase separation above their lower critical solution temperature (LCST) in aqueous solutions. Generally, the LCST is controlled via the polymer−solvent interactions, which, in turn, are highly structure dependent and typically tuned via the polymer side chain. For example, the LCST for the poly(2-oxazoline) family can be tuned via the length and branching of the polymer side chain. In particular, the LCST of poly(2-ethyl-2-oxazoline) varies between 60 and 100 °C, depending on its molar mass, polymer architecture, and concentration. Here, we introduce LCST adjustment via modification of the carbonyl of the amide moiety of poly(2oxazoline)s. We introduce poly(2-ethyl-2-oxazoline-co-N-propiothioacetyl ethylene imine), synthesized from poly(2-ethyl-2oxazoline) using Lawesson's reagent. The degree of thionation of the polymers was varied and characterized by using spectroscopic methods and elemental analysis. While the glass transition temperatures of the copolymers increase with increasing thionation degrees, the decomposition temperatures decrease. Interestingly, polymers with less than 20% thionation degree were soluble in water with LCST behavior. The cloud point temperatures decrease with increasing thionation degree due to the weaker hydrogen bonding ability of thioamides and decreased polarity.

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A molecular dynamics perspective on the cyclization efficiency for poly(2-oxazoline)s and poly(2-oxazine)s

Abstract: The synthesis of cyclic polymers has made tremendous progress over the last decade. However, upscaling remains a challenge. To achieve acceptable cyclization yields, time, and labour intensive screening of experimental...

Cited by 3 publications

References 48 publications

Thionation of poly(2-ethyl-2-oxazoline) and its effect on solubility and cloud point

Thionation of poly(2-ethyl-2-oxazoline) and its effect on solubility and cloud point

Influence of polymer amphiphilicity on the cyclization efficiency of poly(2-oxazoline)s

Thionation of Poly(2-ethyl-2-oxazoline) and Its Effect on Solubility and Cloud Point

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