Polymer thermoreversible gels from organogelators enabled by ‘click’ chemistry

Díaz, David Díaz; Tellado, José Juan Marrero; Velázquez, Daniel García; Ravelo, Ángel G.

doi:10.1016/j.tetlet.2007.12.090

Cited by 39 publications

(24 citation statements)

References 24 publications

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“…Interestingly, stirring a sample of AmDP2 in a CHCl 3 / aqueous ethylenediaminetetraacetic acid (EDTA) biphasic solution for 24 h at 25 8C did not reduce its gelation power, indicating that gelation was not due to cross-linking of the dendronized polymer chains through Cu complexation to the triazole moieties. [6] Moreover, the three ester-linked dendronized polymers EsDP1-EsDP3 were also devoid of gelation properties. Therefore the key structural element that was responsible for gelation must be the amide-linker functionality.…”

Section: Methodsmentioning

confidence: 99%

“…To our knowledge, synthesis of dendronized polymers by AB-type macromonomer polymerization has not been reported before. Moreover, although physical organogels based on dendrimers [4] and linear polymers [5] are known, those based on click poly(triazole) polymers [6] and dendronized polymers [7] are extremely rare.The click macromonomer polymerization is basically a step-growth polymerization. Therefore, to achieve a higher degree of polymerization (DP), it must be ensured that the AB-hetero-bifunctional monomers AmM1-AmM3 are of perfect purity and structural homogeneity.…”

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confidence: 99%

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Dendronized Polymer Organogels from Click Chemistry: A Remarkable Gelation Property Owing to Synergistic Functional‐Group Binding and Dendritic Size Effects

et al. 2008

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The use of 1,3-dipolar cycloaddition reactions between azides and alkynes (click chemistry) has been extremely successful as a versatile synthetic tool to construct novel polymeric systems.[1] Whereas the main thrust has been focused on building up highly elaborate polymeric architectures, such as block copolymers, star polymers, dendrimers, and hyperbranched polymers, it is also noted that the physical properties of such poly(triazole)-based materials are little studied.[1c]Additionally, although there are many examples of the synthesis of dendrimers using click chemistry, only a few concern the preparation of dendronized polymers.[2] These are polymers incorporating multiple dendron segments stemming from a linear polymer backbone and are commonly prepared by graft-to, graft-from, or macromonomer polymerization approaches.[3] The major challenges for these approaches are the difficulty in ensuring complete dendron coverage in the graft-to and graft-from strategies, and the sometimes poor polymerization efficiency in the macromonomer strategy. To improve the synthetic efficacy, it is necessary to make use of reactions that offer perfect conversion efficiency (such as click chemistry). Herein we wish to report a) the successful click synthesis of two different series of dendronized polymers (DPs), AmDP1-AmDP3 and EsDP1-EsDP3, from heterobifunctional amide-linked macromonomers (AmM1-AmM3) and ester-linked macromonomers (EsM1--EsM3), respectively, b) the novel and unique organogelation property of one such poly(triazole)-based dendronized polymer AmDP2, c) the remarkable functionalgroup synergistic effect on polymer interchain H-bonding, owing to the placing of many amide functionalities in close proximity along the polymer chain, and most importantly d) that the macromolecular interactions among the dendronized polymer chains are strongly influenced by the size of dendritic appendages and the nature of the linker functionality. To our knowledge, synthesis of dendronized polymers by AB-type macromonomer polymerization has not been reported before. Moreover, although physical organogels based on dendrimers [4] and linear polymers [5] are known, those based on click poly(triazole) polymers [6] and dendronized polymers [7] are extremely rare.The click macromonomer polymerization is basically a step-growth polymerization. Therefore, to achieve a higher degree of polymerization (DP), it must be ensured that the AB-hetero-bifunctional monomers AmM1-AmM3 are of perfect purity and structural homogeneity. For this purpose, we made use of the symmetrical aliphatic hydrocarbon-based Meldrums acids 1-3[8] as our starting materials. Simple functional-group transformations then led to the target amide-linked macromonomers AmM1-AmM3 in good yields and high purities (see Supporting Information). The macromonomers AmM1-AmM3 were then polymerized in the presence of sodium ascorbate and CuSO 4 in a 1:1:1 solvent mixture of THF, DMF, and water at 25 8C for 4 days. To counteract the poor solubility of the products, DMF was added to m...

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Section: Methodsmentioning

confidence: 99%

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confidence: 99%

Dendronized Polymer Organogels from Click Chemistry: A Remarkable Gelation Property Owing to Synergistic Functional‐Group Binding and Dendritic Size Effects

et al. 2008

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“…The problem with increasing the Cu I amount was the difficulty in perfectly removing the Cu ions because of the presumed interaction of Cu II with the formed triazole products. 32 The residual Cu was indeed detected when the X-ray photoelectron spectroscopy measurement of P1, prepared in the presence of 50 mol% Cu I , was performed (Supplementary Figure S1). Although these remaining Cu ions were thought to interact with the triazole moieties, they did not significantly affect the GPC profiles.…”

Section: Polymer Synthesis and Characterizationmentioning

confidence: 93%

Click synthesis and adhesive properties of novel biomass-based polymers from lignin-derived stable metabolic intermediate

Michinobu

Hiraki

Inazawa

et al. 2011

Polym J

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Novel biomass-based polymers composed of 2-pyrone-4,6-dicarboxylic acid (PDC), which was isolated from lignin as a chemically stable metabolic intermediate, were synthesized by the copper (Cu) (I)-catalyzed, but ligand-free azide-alkyne cycloaddition reaction. The polymerization progress was monitored by the gel permeation chromatography profiles and IR spectroscopies. Very high-molecular-weight polymers with sufficient solubilities in organic solvents were obtained after the polymerization for 70 h, and their chemical structures were fully characterized. The in-situ prepared PDC polymers displayed adhesive properties to various metal surfaces. Among the investigated metals, the tensile strength with Cu, prepared at 70 1C for 4 h, was the highest (3.70 MPa). This specific adhesion to Cu is probably due to the promoted polymerization using the leached Cu I as a catalyst and the crosslinking ability through the interactions with the formed triazole rings. Polymer Journal (2011) 43, 648-653; doi:10.1038/pj.2011.40; published online 11 May 2011Keywords: adhesive; biomass; click chemistry; polyaddition INTRODUCTION Biomass-based renewable materials have attracted considerable attention as a source of green plastics. [1][2][3][4][5] Lignin is a waste biomass that has three-dimensional network structures containing aromatic rings, and its conversion into versatile soluble monomers has been requested. In a previous study, we succeeded in the metabolic conversion of lignin into 2-pyrone-4,6-dicarboxylic acid (PDC) on a large scale via protocatechuate by a transformed bacterium. 6 PDC consists of a polar pseudo-aromatic ring and two carboxylic acids, suggesting the potential use as a bifunctional monomer for polycondensation and polyaddition. As PDC was not accessible from petrochemicals, its chemical reactivity and physical properties were comprehensively investigated. 7-9 During the course of the synthetic studies of PDC polymers, it was found that PDC is unstable under basic conditions. Thus, all the PDC polymers reported so far were synthesized by base-free reactions. In the past few years, a series of PDC polyesters was synthesized by the direct dehydrated polycondensation with various diol co-monomers, and their excellent biodegradable, mechanical and adhesive properties were demonstrated. 10-16 However, the major problem of the PDC polyesters was their relatively low molecular weights. In order to improve the polymer properties, other efficient base-free polymerization methods were desired.

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“…The authors showed that a bis-azide and bis-alkyne formed a soluble linear polymer thus confirming their hypothesis that CuAAC could be used for addition polymerizations (Scheme 5, 24). [24] Further details of this work, along with a recent article by Ravelo and coworkers describing linear CuAAC polymers incorporated into networks (Scheme 5, 25), [25] will be discussed later in the section on network synthesis. In 2005, Angelo and coworkers reported using an iterative diazo-transer/CuAAC process to construct peptidomimetic oligomers that possessed a ''zigzag'' secondary structure resulting from the large dipole moment of the triazole CuAAC product (Scheme 5, 26).…”

Section: Linear ''Click'' Polymers and Oligomers (From Small Moleculementioning

confidence: 99%

“…[25] In this case, however, the CuAAC reaction was performed prior to gelation yielding linear polymers which were then shown to form thermoreversible gels by hydrogen bonding in dimethylsulfoxide (DMSO) and other DMSO-organic solvent mixtures. Interestingly, two unexpected requirements of gel formation were the presence of an SO 2 group on the backbone of the polymers and the presence of some residual copper from the CuAAC reaction.…”

Section: Scheme 24mentioning

confidence: 99%

Construction of Linear Polymers, Dendrimers, Networks, and Other Polymeric Architectures by Copper‐Catalyzed Azide‐Alkyne Cycloaddition “Click” Chemistry

Johnson

Finn

Koberstein

et al. 2008

Macromol. Rapid Commun.

310

159

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The enrichment of materials synthesis with the diverse chemical building blocks and functional groups of small molecule organic chemistry has been greatly accelerated in recent years by the introduction of the copper‐catalyzed azide‐alkyne cycloaddition (CuAAC). The efficiency and modular nature of this unique reaction enables materials chemists to prepare novel functional materials of unprecedented complexity. This review summarizes the application of CuAAC to the field of materials construction, defined here as the preparation of materials with architectural integrity dependent upon the triazole linkage. Recent examples, including linear polymers, dendrimers, polymer networks, polymeric nanoparticles, and other polymeric architectures, are described.magnified image

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Polymer thermoreversible gels from organogelators enabled by ‘click’ chemistry

Cited by 39 publications

References 24 publications

Dendronized Polymer Organogels from Click Chemistry: A Remarkable Gelation Property Owing to Synergistic Functional‐Group Binding and Dendritic Size Effects

Dendronized Polymer Organogels from Click Chemistry: A Remarkable Gelation Property Owing to Synergistic Functional‐Group Binding and Dendritic Size Effects

Click synthesis and adhesive properties of novel biomass-based polymers from lignin-derived stable metabolic intermediate

Construction of Linear Polymers, Dendrimers, Networks, and Other Polymeric Architectures by Copper‐Catalyzed Azide‐Alkyne Cycloaddition “Click” Chemistry

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