Triazolinediones as Highly Enabling Synthetic Tools

Bruycker, Kevin De; Billiet, Stijn; Houck, Hannes A.; Chattopadhyay, Subrata; Winne, Johan M.; Prez, Filip E. Du

doi:10.1021/acs.chemrev.5b00599

Cited by 172 publications

(178 citation statements)

References 340 publications

Supporting

Mentioning

177

Contrasting

Unclassified

Order By: Relevance

“…While the “grafting from” procedure with atom transfer radical polymerization proved to be an effective access strategy to bottle brushes, an interference of the CRP process with the diselenide bridges was evident (data not shown). Therefore, a “grafting onto” approach was chosen by exploiting triazolinedione (TAD) − diene cycloaddition reaction to graft poly( n‐ butyl acrylate) (PnBuA) side chains onto the folded macromolecule backbone [Fig. (A)] …”

Section: Resultsmentioning

confidence: 99%

Molecular Bottle Brushes with Positioned Selenols: Extending the Toolbox of Oxidative Single Polymer Chain Folding with Conformation Analysis by Atomic Force Microscopy

Schué

Kopyshev

Lutz

et al. 2019

Journal of Polymer Science

View full text Add to dashboard Cite

A synthesis route to controlled and dynamic single polymer chain folding is reported. Sequence‐controlled macromolecules containing precisely located selenol moieties within a polymer chain are synthesized. Oxidation of selenol functionalities lead to diselenide bridges and induces controlled intramolecular crosslinking to generate single chain collapse. The cyclization process is successfully characterized by SEC as well as by 1H NMR and 2D HSQC NMR spectroscopies. In order to gain insight on the molecular level to reveal the degree of structural control, the folded polymers are transformed into folded molecular brushes that are known to be visualizable as single molecule structures by AFM. The “grafting onto” approach is performed by using triazolinedione−diene reaction to graft the side chain polymers. A series of folded molecular brushes as well as the corresponding linear controls are synthesized. AFM visualization is proving the cyclization of the folded backbone by showing globular objects, where non‐folded brushes show typical worm‐like structures. © 2019 Wiley Periodicals, Inc. J. Polym. Sci. 2020, 58, 154–162

show abstract

Section: Resultsmentioning

confidence: 99%

Molecular Bottle Brushes with Positioned Selenols: Extending the Toolbox of Oxidative Single Polymer Chain Folding with Conformation Analysis by Atomic Force Microscopy

Schué

Kopyshev

Lutz

et al. 2019

Journal of Polymer Science

View full text Add to dashboard Cite

show abstract

“…The synthesis of functionalized TAD compounds can be challenging, 29 but here we introduce a novel and readily accessible dye-containing TAD reagent bearing an azobenzene-type chromophoric unit. The brightly orange 4-azobenzene urazole ( 11 , Scheme 4) can be easily obtained in a three-step synthesis from commercial 4-aminoazobenzene.…”

Section: Resultsmentioning

confidence: 99%

“…29 An alternative approach can be offered by first reacting the TAD moiety with a suitable blocking agent that can be removed in a later stage. 24 The newly developed 2-phenylindoles are attractive blocking agents for this purpose, as they give bench-stable adducts 13 and 14 (Scheme 4) that release TAD moieties in a controlled fashion upon heating, wherein the release temperature can be controlled by judiciously choosing the indole reaction partner ( cf.…”

Section: Resultsmentioning

confidence: 99%

Design of a thermally controlled sequence of triazolinedione-based click and transclick reactions

et al. 2017

Self Cite

View full text Add to dashboard Cite

show abstract

“…Furthermore, we used the efficient, recently revisited "click chemistry" of 1,2,4-triazoline-3,5-diones (TAD) 17,18 to modify the double bonds along the PPE backbone to further adjust the material properties. This TADene chemistry can not only be applied as a reliable and convenient post-modification reaction of unsaturated polymers but will also introduce additional nitrogen atoms into the PPEs, which is expected to have a positive influence on their flame retardant performance.…”

mentioning

confidence: 99%

Triazolinedione-“clicked” poly(phosphoester)s: systematic adjustment of thermal properties

et al. 2017

Self Cite

View full text Add to dashboard Cite

The thermal properties of halogen-free flame retardant poly(phosphoester)s from acyclic diene metathesis polycondensation have been optimized by a systematic post-modification using 1,2,4-triazoline-3,5-dione derivatives. The straightforward modification not only increased their glass transition temperatures significantly but also improved the thermal stability with respect to their char yields.Poly( phosphoester)s (PPEs) can be prepared via both ringopening polymerization and polycondensation.1,2 We recently applied ADMET polycondensation to prepare a variety of PPEs. [3][4][5][6] Currently, PPEs are studied in biomedical applications for their biocompatibility, 7 biodegradability and adjus- show higher resistance to leaching and migration, compared to low molecular weight additives. 9 Indeed, phosphorus is an efficient char promoter forming an accumulated protective layer on the materials surface, which limits the release of fuel to the flame. 10,11 Additionally, PPEs typically show low toxicity or almost smoke-free burning. 12,13 Recently, the combination of phosphorus-containing flame retardants with nitrogen compounds has attracted much attention. The combination of both elements physically and chemically can dramatically improve the action of the phosphorus species in the condensed phase upon combustion. 14,15 Nitrogen compounds are believed to act by the release of inert gases or by the promotion of char formation as a result of a condensation reaction.Besides phosphorus and nitrogen, the introduction of aromatic structures is also often mentioned to promote the charring. 16As a systematic study on the thermal properties and char yield, with structural variation of the main-and side chains of PPEs, is missing in the current literature, the main goal of this research was the preparation of modified PPEs via ADMET polycondensation, as a result of the variation of both the backbone and side chains. Furthermore, we used the efficient, recently revisited "click chemistry" of 1,2,4-triazoline-3,5-diones (TAD) 17,18 to modify the double bonds along the PPE backbone to further adjust the material properties. This TADene chemistry can not only be applied as a reliable and convenient post-modification reaction of unsaturated polymers but will also introduce additional nitrogen atoms into the PPEs, which is expected to have a positive influence on their flame retardant performance. TADs are one of the most reactive (di)enophiles and show quantitative conversions at room temperature with isolated alkenes or conjugated dienes, respectively in an Alder-ene or Diels-Alder reaction. TAD has recently been applied in a wide range of applications, such as self-healing, 19 surface chemistry, 20-22 and post-modification of unsaturated ADMET polymers. 23This is the first report on the post-modification of PPEs via their internal double bonds for tuning their thermal properties. Supposing that TAD-modification can increase the glass transition temperature (T g ), this would undoubtedly broaden the range of applications for PPEs...

show abstract

Triazolinediones as Highly Enabling Synthetic Tools

Cited by 172 publications

References 340 publications

Molecular Bottle Brushes with Positioned Selenols: Extending the Toolbox of Oxidative Single Polymer Chain Folding with Conformation Analysis by Atomic Force Microscopy

Molecular Bottle Brushes with Positioned Selenols: Extending the Toolbox of Oxidative Single Polymer Chain Folding with Conformation Analysis by Atomic Force Microscopy

Design of a thermally controlled sequence of triazolinedione-based click and transclick reactions

Triazolinedione-“clicked” poly(phosphoester)s: systematic adjustment of thermal properties

Contact Info

Product

Resources

About