Sequential Reactions for Post-polymerization Modifications

Moldenhauer, Fenja; Théato, Patrick

doi:10.1007/12_2015_312

Cited by 13 publications

(8 citation statements)

References 75 publications

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“…Therefore, a postpolymerization functionalization has to be utilized in order to introduce the histidine moieties into the copolymer. Theato and co‐workers presented a versatile method for the substitution of an active pentafluorophenyl ester with free amine functionalities . Thus, this postpolymerization procedure was also applied in our case to form well‐defined histidine‐rich copolymers (Scheme ).…”

Section: Resultsmentioning

confidence: 97%

Histidine–Zinc Interactions Investigated by Isothermal Titration Calorimetry (ITC) and their Application in Self‐Healing Polymers

Enke

Jehle

Bode

et al. 2017

Macro Chemistry & Physics

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Histidine-zinc interactions are believed to play a key role in the self-healing behavior of mussel byssal threads due to their reversible character. Taking this as inspiration, the authors synthesize here histidine-rich copolymers, as well as model histidine compounds and characterize them using isothermal titration calorimetry (ITC). With this approach, the influence of two different zinc(II) salts and the role in the complex formation of the amine function of the imidazole ring are investigated in detail. The extracted metal-ligand ratios are utilized to design novel self-healing metallopolymers. For this purpose, n-lauryl methacrylate is copolymerized with the histidine monomer via reversible addition-fragmentation chain transfer polymerization. The copolymers are crosslinked using different zinc salts, and the resulting coatings are characterized with Raman spectroscopy to investigate the metal coordination behavior and with scratch healing tests to investigate the self-healing capacity. Finally, the selfhealing behavior of the different materials is correlated with the metal-ligand binding affinity measured by ITC. 2 (2.5 g, 5.52 mmol) was dissolved in 40 mL dry dichloromethane. Triethylamine (1.53 mL, 11.06 mmol) and acetic anhydride (0.52 mL, 5.52 mmol) was added dropwise. After complete conversion, which was monitored by thin layer chromatography (TLC), the solvent and the triethylamine were evaporated in vacuo. The residue was dissolved in 50 mL chloroform and washed with 0.1 m NaHCO 3 solution and afterward with deionized water. The organic layer was dried over Na 2 SO 4 . Finally, the crude product was purified by silica gel chromatography (MeOH/CHCl 3 1:9, R f = 0.5).Yield: 2.0 g (4.04 mmol) of a white solid, 73%. Melting point: 76-77 °C. 1 H NMR (300 MHz, CDCl 3 ): δ = 0.85-0.89 (t, 3H, CH 3 ), 1.22-1.46 (m, 4H, CH 2 CH 2 CH 3 ), 1.93-2.04 (m, 4H, CH 3 Macromol. Chem. Phys. , , 1600458 M. Enke et al.

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Section: Resultsmentioning

confidence: 97%

Histidine–Zinc Interactions Investigated by Isothermal Titration Calorimetry (ITC) and their Application in Self‐Healing Polymers

Enke

Jehle

Bode

et al. 2017

Macro Chemistry & Physics

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“…Azide-functional vinyl monomers, although found throughout the literature, have been shown to undergo cycloaddition reactions with vinyl groups . Consequently, additional postpolymerization modifications can be needed to facilitate click reactions. − …”

Section: Introductionmentioning

confidence: 99%

Azide–para-Fluoro Substitution on Polymers: Multipurpose Precursors for Efficient Sequential Postpolymerization Modification

Noy

Smolan

et al. 2019

Macromolecules

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The 2,3,4,5,6-pentafluorobenzyl group has become a popular reactive functionality in polymer chemistry because of its high susceptibility to para-fluoro substitution with thiols. Herein, it is demonstrated postpolymerization that the para-fluoride can be substituted using sodium azide and that the resulting 4-azido-2,3,5,6tetrafluorobenzyl-functional polymers are versatile precursors for a multitude of onward modifications with click-like efficiencies. Quantitative azide−para-fluoro substitution was found for poly-(2,3,4,5,6-pentafluorobenzyl methacrylate) and the related Passerini ester−amide (meth)acrylic (co)polymers when heated in DMF with sodium azide to 80 °C for 60−90 min. Conversely, the azidation of poly(2,3,4,5,6-pentafluorostyrene) under similar conditions resulted in ∼90% substitution efficiency. Azidefunctional (co-)polymers were thermally stable below 100 °C and were subsequently modified with (i) four different alkynes (CuBr, triethylamine, DMF, 55 °C, overnight) to give 1,4-substituted 1,2,3-triazoles in >95% conversions; (ii) potassium thioacetate (DMF, RT, 15 min) with quantitative amidation to the acetanilide derivative; and (iii) DL-dithiothreitol (methanol/ DMF, RT, 90 min), resulting in complete reduction of the azides to primary amines, which were subsequently acylated with two different acyl chlorides. Products were characterized by 1 H NMR, 19 F NMR, Fourier transform infrared spectroscopies, and size exclusion chromatography. Given their adaptability, perfluorophenylazides have huge potential as multipurpose intermediates in polymer and materials chemistry.

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“…As a result, imparting more than one functional group per repeat unit has proven challenging, and only a limited variety of chemical transformations (e.g., azide–alkyne cycloaddition, thiol–ene/yne chemistry) have been commonly employed . The challenge of incorporating multiple functionalities per repeat unit has compelled many research groups to explore efficient synthetic routes to multifunctional homopolymers. − For example, polymers containing glycidyl groups allow multifunctionalization by sequentially reacting the epoxide with a nucleophile and then functionalizing with an electrophile. − This synthetic strategy has also been applied to the preparation of various polymeric topologies such as hydrogels, hyperbranched polymers, and polymer brushes . Kakuchi and Theato performed efficient, sequential sulfoamidation–Mitsunobu reactions using two nucleophiles (i.e., amines followed by alcohols) to prepare multifunctional homopolymers .…”

Section: Introductionmentioning

confidence: 99%

Multifunctional Homopolymers: Postpolymerization Modification via Sequential Nucleophilic Aromatic Substitution

et al. 2016

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Despite recent progress for efficient and precise synthesis of functional polymers, few reports describe postpolymerization functionalization strategies for the controlled incorporation of multiple pendent groups per repeat unit. Cyanuric chloride, or 2,4,6-trichloro-1,3,5-triazine (TCT), offers a facile method to introduce distinct pendent functionalities. An acrylamide monomer containing a triazine ring with two electrophilic sites was prepared from TCT and polymerized via reversible addition−fragmentation chain transfer (RAFT) polymerization. Subsequent nucleophilic aromatic substitution reactions using a combination of amine and thiol nucleophiles introduced two functionalities into each repeat unit of the RAFTderived polymers. The success of each postpolymerization modification reaction was confirmed by 1 H NMR spectroscopy and size-exclusion chromatography, and small molecule model studies corroborated the high chemoselectivity of the nucleophilic aromatic substitution reactions. This postpolymerization modification strategy based on TCT enables a facile and efficient synthesis of multifunctional homopolymers.

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Sequential Reactions for Post-polymerization Modifications

Cited by 13 publications

References 75 publications

Histidine–Zinc Interactions Investigated by Isothermal Titration Calorimetry (ITC) and their Application in Self‐Healing Polymers

Histidine–Zinc Interactions Investigated by Isothermal Titration Calorimetry (ITC) and their Application in Self‐Healing Polymers

Azide–para-Fluoro Substitution on Polymers: Multipurpose Precursors for Efficient Sequential Postpolymerization Modification

Multifunctional Homopolymers: Postpolymerization Modification via Sequential Nucleophilic Aromatic Substitution

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