Revisiting thiol‐yne chemistry: Selective and efficient monoaddition for block and graft copolymer formation

Sprafke, Johannes K.; Spruell, Jason M.; Mattson, Kaila M.; Montarnal, Damien; McGrath, Alaina J.; Pötzsch, Robert; Miyajima, Daigo; Hu, Jerry; Latimer, Allegra A.; Voit, Brigitte; Aida, Takuzo; Hawker, Craig J.

doi:10.1002/pola.27345

Cited by 20 publications

(14 citation statements)

References 48 publications

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“…SR networks were prepared through a modified one‐pot strategy involving a photo‐initiated thiol‐yne reaction of DP‐PEG with monothiolated β‐cyclodextrin (CDSH) as a sliding cross‐linker and HPCD as a sliding spacer (Scheme ) . HPCD was chosen as the inert macrocyclic spacer due to its high solubility (>600 mg/ml) in water and lack of cross‐reactivity during network formation .…”

Section: Resultsmentioning

confidence: 99%

Structural Versatility in Slide‐Ring Gels: Influence of Co‐Threaded Cyclodextrin Spacers

Murakami

Schmidt

Brown

et al. 2017

J. Polym. Sci. Part A: Polym. Chem.

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We describe a one-pot strategy for the fabrication of novel slide-ring (SR) gels based on supramolecular polyrotaxane structures with cyclodextrin-derived cross-links and additional free cyclodextrin ring spacers co-threaded onto the polymer backbones. Photoinitiated thiol-yne click coupling leads to facile hydrogel fabrication from pseudo-polyrotaxanes prepared in situ from b-cyclodextrin derivatives and bifunctional polyethylene glycol (PEG). The obtained SR gels were characterized by NMR spectroscopy using a polyrotaxane model compound with the ratio of cyclodextrin sliding spacers to PEG backbone controlled by adjusting the feed ratio of the starting materials. This structural tuning leads to dramatic changes in the rheological properties, mechanical properties, and swelling behavior of the SR gels. In addition, the coupling of simple synthetic procedures with enhanced properties offers a versatile approach to novel elastomeric materials.

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Section: Resultsmentioning

confidence: 99%

Structural Versatility in Slide‐Ring Gels: Influence of Co‐Threaded Cyclodextrin Spacers

Murakami

Schmidt

Brown

et al. 2017

J. Polym. Sci. Part A: Polym. Chem.

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“…Our initial efforts focused on adapting this small‐molecule chemistry for polyether functionalization (Supporting Information Scheme S2). After derivatizing the TES‐protected catechol, making it amendable to thiol‐ene chemistry ( 5 ) (initial studies utilized ethane dithiol), we then coupled it to a P(EO‐ co ‐AGE)‐ b ‐PEO‐ b ‐P(EO‐ co ‐AGE) triblock copolymer. Unfortunately, gel permeation chromatography (GPC) showed a dramatic increase in dispersity as well as the formation of a significant amount of high molecular weight byproduct [Fig.…”

Section: Resultsmentioning

confidence: 99%

A facile synthesis of catechol‐functionalized poly(ethylene oxide) block and random copolymers

Mattson

Latimer

McGrath

et al. 2015

J. Polym. Sci., Part A: Polym. Chem.

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Herein we develop a facile synthetic strategy for the functionalization of well‐defined polyether copolymers with control over the number and location of catechol groups. Previously, the functionalization of polyethylene oxide (PEO)‐based polymers with catechols has been limited to functionalization of the chain ends only, hampering the synthesis of adhesive and antifouling materials based on this platform. To address this challenge, we describe an efficient and high‐yielding route to catechol‐functionalized polyethers, which could allow the effects of polymer architecture, molecular weight, and catechol incorporation on the adhesive properties of surface‐anchored PEO to be studied. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2015, 53, 2685–2692

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“…Though, thiol-ene and thiol-yne click reactions have found numerous applications in polymer chemistry, they found limited practice [99] in the synthesis of block copolymers. The challenges [100] regarding the efficient coupling of large polymer chains remain as drawbacks during successful implementation of thiol-ene reactions and need more elaborated research.…”

Section: Block Copolymersmentioning

confidence: 99%

Click Chemistry in Macromolecular Design: Complex Architectures from Functional Polymers

Arslan

Taşdelen

2018

Chemistry Africa

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This contribution reviews the applications of click chemistry reactions in design and synthesis of various macromolecular architectures that hold key aspects in polymer science. By considering the emerging concepts that shape how synthetic polymer chemistry and macromolecular engineering utilize 'reactions' in 'fabrication', in the last decade, the click chemistry methodologies have been pioneered the chemical approaches that allow to access diverse complex macromolecules. The common and leading features of click chemistry reactions rely on efficient, fast, selective and easy to implement chemical transformations giving very high to quantitative coupling efficiencies. These are essential virtues that provide triumphing in macromolecular engineering, since the building blocks are usually large polymer chains. For the efficient building of complex macromolecules via click reactions, properly functionalized polymers are key components in which special design is required to successful installation of 'clickable' reactive groups on polymer end groups or side chains. In this report, the synthetic methods encompassing various click chemistry reactions in fabrication and applications of a range of complex macromolecular architectures have been reviewed.

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Revisiting thiol‐yne chemistry: Selective and efficient monoaddition for block and graft copolymer formation

Cited by 20 publications

References 48 publications

Structural Versatility in Slide‐Ring Gels: Influence of Co‐Threaded Cyclodextrin Spacers

Structural Versatility in Slide‐Ring Gels: Influence of Co‐Threaded Cyclodextrin Spacers

A facile synthesis of catechol‐functionalized poly(ethylene oxide) block and random copolymers

Click Chemistry in Macromolecular Design: Complex Architectures from Functional Polymers

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