Synthesis and characterization of a photo-crosslinkable polyurethane based on a coumarin-containing polycaprolactone diol

Rivero, R. Seoane; Solaguren, Pilar Bilbao; Zubieta, Koldo Gondra; González-Jiménez, Antonio; Valentín, Juan López; Marcos‐Fernández, Ángel

doi:10.1016/j.eurpolymj.2016.01.047

Cited by 30 publications

(31 citation statements)

References 43 publications

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“…The synthesis of the coumarin diol (CD) was carried out following the procedure of Seoane Rivero et al with some modifications.…”

Section: Methodsmentioning

confidence: 99%

“…In this sense, coumarin derivatives present antioxidant activity, thus coumarin can increase the thermal stability of the final PUs . They have been employed as hard segments in polyethylene glycol (PEG)‐based PUs, and also in PCL‐based PUs . Although coumarins have all the previously mentioned advantages, it has been shown that when introducing monohydroxyl‐coumarin derivatives into polyurethane networks as chain‐end crosslinkable groups, low photo‐conversion degrees are observed since the coumarin moieties have a low probability of reaching each other to photo‐dimerize .…”

Section: Introductionmentioning

confidence: 99%

“…Although coumarins have all the previously mentioned advantages, it has been shown that when introducing monohydroxyl‐coumarin derivatives into polyurethane networks as chain‐end crosslinkable groups, low photo‐conversion degrees are observed since the coumarin moieties have a low probability of reaching each other to photo‐dimerize . Thus, the use of dihydroxyl‐coumarin based species offers the opportunity to synthesize PUs in which the coumarin moieties are within the polymeric chains, which will give the final material a higher responsiveness to light . However, it has been observed during the one‐step polycondensation that, although di‐substituted coumarin are formed, mono‐substituted species are also frequent, leading to polyurethanes with lower molecular weights and high polydispersity indexes .…”

Section: Introductionmentioning

confidence: 99%

“…Thus, the use of dihydroxyl‐coumarin based species offers the opportunity to synthesize PUs in which the coumarin moieties are within the polymeric chains, which will give the final material a higher responsiveness to light . However, it has been observed during the one‐step polycondensation that, although di‐substituted coumarin are formed, mono‐substituted species are also frequent, leading to polyurethanes with lower molecular weights and high polydispersity indexes . In this sense, it is known that the PUs obtained from the synthesis of a pre‐polymer have higher molecular weights than those prepared by one‐step reactions.…”

Section: Introductionmentioning

confidence: 99%

“…1 H NMR (400 MHz, CDCl 3 ): δ = 7.51 (d, 1H; J = 8.8 Hz), 6.87 (dd, 1H; J1 = 8.8 Hz, J2 = 2.4 Hz), 6.83 (d, 1H, J = 2.4 Hz), 6.15 (d, 1H, J = 1.2 Hz), 4.56 (t, 2H, J = 4.8 Hz), 4.27 (t, 2H, J = 4.8 Hz), 3.92 (d, 2H, J = 11.2 Hz), 3.74 (d, 2H, J = 11.2 Hz), 2.40 (d, 3H, J = 1.2 Hz), 1.08 (s, 3H) …”

mentioning

confidence: 99%

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Influence of Poly(ε‐caprolactone) Molecular Weight and Coumarin Amount on Photo‐Responsive Polyurethane Properties

Salgado

Arrieta

Peponi

et al. 2016

Macro Materials & Eng

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Photo‐reversible polyurethane (PU) coatings based on coumarin diol (CD) are obtained. Initially, pre‐polymers based on different amounts of coumarin (5, 15, and 25 mol%) and 1,6‐hexamethylene diisocyanate are prepared to obtain PUs with a large incorporation of CD and high molecular weight. The pre‐polymer is posterior reacted with poly(ε‐caprolactone) diol (PCL‐diol), either with molecular weight trueM¯n = 530 or 2000 g mol–1. The thermal stabilities of the PUs are studied using thermogravimetric analysis. Polymers with a higher content of CD present higher stability. The thermal transitions and the mechanical response are analyzed using differential scanning calorimetry and strain‐stress tests, respectively. Moreover, the photo‐reversibility of CD‐based PUs is followed by UV absorption. In general, photo‐dimerization induces better mechanical properties of the final PUs. Materials obtained with short PCL‐diol (trueM¯n = 530 g mol–1) and the highest amount of CD present higher reversibility processes. Therefore, these polymers are promising for application as coating systems.

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“…The synthesis of the coumarin diol (CD) was carried out following the procedure of Seoane Rivero et al with some modifications.…”

Section: Methodsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

mentioning

confidence: 99%

See 3 more Smart Citations

Influence of Poly(ε‐caprolactone) Molecular Weight and Coumarin Amount on Photo‐Responsive Polyurethane Properties

Salgado

Arrieta

Peponi

et al. 2016

Macro Materials & Eng

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Synthesis of Polyacrylate‐Based Polyurethane by Organocatalyzed Group Transfer Polymerization and Polyaddition

Liu

Jia

Ding

et al. 2020

Macro Chemistry & Physics

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The current work describes the synthesis of novel polyacrylate‐based polyurethanes through the polyaddition of hexamethylene diisocyanate (HDI) with α,ω‐hydroxyl end‐functionalized polyacrylates (HO‐PA‐OHs), including α,ω‐hydroxyl end‐functionalized poly(n‐butyl acrylate) (HO‐PnBA‐OH), poly(n‐octyl acrylate) (HO‐PnOA‐OH), and poly(n‐lauryl acrylate) (HO‐PnLA‐OH), respectively. HO‐PA‐OHs are prepared by the N‐(trimethylsilyl)bis(trifluoromethanesulfonyl)imide (Me3SiNTf2)‐catalyzed group transfer polymerizations (GTPs) of n‐butyl acrylate (nBA), n‐octyl acrylate (nOA), and n‐lauryl acrylate (nLA) in toluene at room temperature using the functional 1‐(2‐triisopropylsiloxyethoxy)‐1‐triisopropylsiloxy‐2‐methyl‐1‐propene as an initiator and the low ceiling temperature acrylate, 2‐(triisopropylsiloxy)ethyl α‐phenylacrylate, as a terminator, followed by the desilylation of the resulting α,ω‐triisopropylsiloxy end‐functionalized polyacrylates (iPr3SiO‐PA‐OSiiPr3s) using tetra‐n‐butylammonium fluoride (TBAF). The polyaddition reactions between HO‐PA‐OHs and HDI are carried out in toluene using 1,8‐diazabicyclo[5.4.0]undec‐7‐ene (DBU) as the catalyst to afford the target polyacrylate‐based polyurethanes. The polymer structures are characterized by 1H NMR spectroscopy and FT‐IR measurements. The thermal properties of the resulting polyacrylate‐based polyurethanes are investigated by differential scanning calorimeter.

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Harnessing the Photoperformance of N‐Methyl‐Quinolinone for Gated Photo‐Driven Cyclability and Reversible Photoligation

Streicher,

Stamp,

Kluth

et al. 2024

Macromol. Rapid Commun.

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Abstract[2π + 2π]‐photocycloadditions and their ability to trigger controlled and reversible photoligation through disparate wavelengths provide an attractive platform to unlock advanced functionalities in soft materials. Yet, among the limited amount of functional motifs enabling reversible photoreactions, cyclability is often overlooked due to poor reaction yield and orthogonality. In this study, the advantageous photocharacteristics of the previously underexplored N‐methyl‐quinolinone photoresponsive motif are leveraged to create a covalent gated system, enabling controlled formation and cleavage of covalent bonds on demand. A systematic evaluation of individual cycloadditions and reversions on the molecular scale, including reaction rates, conversions, and photoproducts, allows identification of the required conditions for generating controlled photoreactions with a remarkable degree of cyclability; while, maintaining high reaction yields. Ultimately, these controlled and cyclable reactions are translated to a macromolecular scale, showcasing a comparable performance in initiating reversible photoligation, as observed at the molecular level. In addition, it is also shown that this progressive methodology can be leveraged to gain a comprehensive understanding of cyclability and clarify the factors contributing to its decreasing yield. Overall, unlocking the potential of quinolinone derivatives through this step‐by‐step approach lays the foundation for the development of highly controlled and responsive polymer materials with unprecedented potential.

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Synthesis and characterization of a photo-crosslinkable polyurethane based on a coumarin-containing polycaprolactone diol

Cited by 30 publications

References 43 publications

Influence of Poly(ε‐caprolactone) Molecular Weight and Coumarin Amount on Photo‐Responsive Polyurethane Properties

Influence of Poly(ε‐caprolactone) Molecular Weight and Coumarin Amount on Photo‐Responsive Polyurethane Properties

Synthesis of Polyacrylate‐Based Polyurethane by Organocatalyzed Group Transfer Polymerization and Polyaddition

Harnessing the Photoperformance of N‐Methyl‐Quinolinone for Gated Photo‐Driven Cyclability and Reversible Photoligation

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