Effect of H-bonding on network junction and macroscopic elastomer properties in photocured polyacrylate films

Wu, Bing; Chassé, Walter; Heise, Andreas; Kentgens, A.P.M.; Brougham, Dermot F.; Litvinov, V. M.

doi:10.1039/d1qm01535d

Cited by 5 publications

(5 citation statements)

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“…The variations in chain conformation are largest for acrylates with BM1a/FM1a, BM2/FM2, or BM3/FM3 representing relatively flexible polymer chains, while the variations are less pronounced for the BM1b/FM1b monomers with a more compact and stiff cyclic molecular structure. As outlined in previous works, 66 the molecular interactions through hydrogen bonding may influence structural organization and local arrangement in a polyacrylate network, which is consequently reflected in macroscopic mechanical properties. The slight differences in hydrogen bonding interactions for crosslinked BM and FM monomers are indeed revealed at 3200 to 3500 cm −1 wavenumbers.…”

Section: Resultsmentioning

confidence: 86%

(Thermo)mechanical and chemical characteristics of photochemically crosslinked acrylates from bio‐ and fossil‐based origin

Samyn,

Adeel,

Pazdur

et al. 2024

Journal of Polymer Science

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The acrylates with oligomers and monomers from (partially) bio‐based feedstock become available at (semi‐)industrial scale, which can be processed through photochemical crosslinking for applications in coatings, additive manufacturing, electronics, or inks. Although fossil‐ and bio‐based acrylates may have a similar chemical composition, it requires good understanding of processing and structure–property relationships as minor changes in microstructure may strongly alter the performance. A comparative study on mechanical properties and chemical structure of bio‐ and fossil‐based acrylates with different functionalities and backbone structures reveals higher ductility of bio‐based acrylates, in relation with a more complex organization of the intrinsic molecular structure. The latter is confirmed by mechanical testing and visco‐elastic characteristics (dynamic mechanical analysis) yielding lower stiffness and higher dampening of bio‐based acrylates, in parallel with a lower glass transition temperature (differential scanning calorimetry). The complex molecular arrangements include a nanoscale morphology with ordered structure (X‐ray diffraction), conformational changes (infrared spectroscopy), and a residual high‐molecular weight fraction (size exclusion chromatography). The visco‐elastic calculations indicate only 4% to 5% lower crosslinking density and around 10% higher mean molar mass of the polymer chains segments between chemical crosslinks and trapped chain entanglements, which explain the unique structure and performance of bio‐based acrylates.

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Section: Resultsmentioning

confidence: 86%

(Thermo)mechanical and chemical characteristics of photochemically crosslinked acrylates from bio‐ and fossil‐based origin

Samyn,

Adeel,

Pazdur

et al. 2024

Journal of Polymer Science

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“…Functionalized PEI contains hydroxy groups and a higher percentage of secondary amines, which results in stronger hydrogen bonds between the amines and hydroxy groups. Hydrogen bonds are also known to influence the mobility of chains in various polymeric systems. − It was reported by Li et al that in aminopolymers, hydrogen bonds involving hydroxy groups impart higher stability and longer lifetimes and are less prone to bond breakage and reformation. This effect is more pronounced when the amine involved in hydrogen bonding is a secondary amine.…”

Section: Resultsmentioning

confidence: 99%

Glycidyl Ether-Functionalized Poly(ethylenimine)-Impregnated Sorbents for CO₂ Capture from Ultradilute Sources

Shaikh,

Didas,

Sakwa-Novak

et al. 2024

ACS Appl. Polym. Mater.

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Carbon dioxide adsorbents based on branched poly(ethylenimine) (PEI) are prevalent in postcombustion CO 2 capture as well as direct air capture (DAC) of CO 2 . In DAC, PEI-based sorbents offer good tolerance to ranging environmental conditions (temperature, relative humidity, etc.) but require moderate temperature swings for CO 2 desorption and oxidize over extended cycling in oxidative environments, such as ambient air. In this work, the functionalization of branched PEI with epoxides and glycidyl ethers of varying chain lengths is demonstrated, and the CO 2 sorption characteristics of the resulting alumina-supported sorbents are elucidated. In parallel, the oxidative stability of the sorbents is probed using short, intense oxidative treatments, followed by measurement of the retained CO 2 sorption capacities after oxidation. Functionalization of PEI in all cases leads to improved oxidative stability with a modest impact on CO 2 uptake performance, with noteworthy performance when using long-chain glycidyl ethers or epoxides. Glycidyl ether-functionalized PEIs, which contain an additional ether linkage as compared to the epoxidefunctionalized samples, allow for lower regeneration temperatures, offering promise for practical use compared to pristine PEI and epoxide-PEI sorbents.

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“…18 Hydrogen bonding has been found to impact chain mobility in various polymer systems. [19][20][21] Our previous studies on PEI and aminooligomers underscore the importance of radical reactions in degradation. 14,22 These findings hint at potential connections between epoxide-functionalization, hydrogen bonding, polymer mobility, and degradation kinetics of amine sorbents.…”

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confidence: 93%

Enhanced Hydrogen Bonding via Epoxide-functionalization Restricts Mobility in Poly(ethylenimine) for CO2 Capture

Li,

Andrade,

Varni

et al. 2023

Preprint

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Epoxide-functionalization has emerged as an effective strategy for enhancing the oxidative stability of poly(ethylenimine)-based CO2 capture sorbents. However, the underlying mechanism remains largely unexplored. Here we combine first-principles modeling, material synthesis, and characterizations to investigate the impact of epoxide-functionalization on hydrogen bonding and mobility in poly(ethylenimine) (PEI). Blue-moon ensemble and deep potential molecular dynamics simulations reveal that epoxide-functionalization leads to stronger hydrogen bonding involving hydroxyl groups. Synthesized branched PEI samples with and without propylene-oxide (PO) functionalization are characterized using DSC, NMR relaxometry, and fluorescent probes, demonstrating that PO-functionalization significantly reduces BPEI mobility. These findings suggest that the enhanced oxidative stability of epoxide-functionalized PEI can be attributed to the formation of strong hydrogen bonds with hydroxyl groups, which restrict the mobility of PEI and decelerate mobility-dependent radical propagation reactions responsible for polymer degradation. Strategies for further tuning hydrogen bond environment are proposed based on these findings.

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Effect of H-bonding on network junction and macroscopic elastomer properties in photocured polyacrylate films

Abstract: Two series of polyacrylate films with different H-bonding capable monoacrylate copolymers were synthesized by UV-initiated photo-polymerization. Detailed IR analyses on cured samples show that networks made from structurally distinguishable mono-acrylate...

Cited by 5 publications

References 50 publications

(Thermo)mechanical and chemical characteristics of photochemically crosslinked acrylates from bio‐ and fossil‐based origin

(Thermo)mechanical and chemical characteristics of photochemically crosslinked acrylates from bio‐ and fossil‐based origin

Glycidyl Ether-Functionalized Poly(ethylenimine)-Impregnated Sorbents for CO₂ Capture from Ultradilute Sources

Enhanced Hydrogen Bonding via Epoxide-functionalization Restricts Mobility in Poly(ethylenimine) for CO2 Capture

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Effect of H-bonding on network junction and macroscopic elastomer properties in photocured polyacrylate films

Abstract: Two series of polyacrylate films with different H-bonding capable monoacrylate copolymers were synthesized by UV-initiated photo-polymerization. Detailed IR analyses on cured samples show that networks made from structurally distinguishable mono-acrylate...

Cited by 5 publications

References 50 publications

(Thermo)mechanical and chemical characteristics of photochemically crosslinked acrylates from bio‐ and fossil‐based origin

(Thermo)mechanical and chemical characteristics of photochemically crosslinked acrylates from bio‐ and fossil‐based origin

Glycidyl Ether-Functionalized Poly(ethylenimine)-Impregnated Sorbents for CO2 Capture from Ultradilute Sources

Enhanced Hydrogen Bonding via Epoxide-functionalization Restricts Mobility in Poly(ethylenimine) for CO2 Capture

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Product

Resources

About

Glycidyl Ether-Functionalized Poly(ethylenimine)-Impregnated Sorbents for CO₂ Capture from Ultradilute Sources