Sweet supramolecular elastomers from α,ω-(β-cyclodextrin terminated) PDMS

Rambarran, Talena; Bertrand, Arthur; Gonzaga, Ferdinand; Boisson, Fernande; Bernard, Julien; Fleury, Étienne; Ganachaud, François; Brook, Michael A.

doi:10.1039/c6cc02632j

Cited by 20 publications

(18 citation statements)

References 63 publications

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“…Rambarran et al. showed that, following the PR reaction, Huisgen or azide/alkyne click reactions could be used to create silicone/PEG (or cyclodextrin) surfactants (Figure B), elastomers (Figure C), copolymers or adhesives . The most important orthogonal reaction in silicone systems is platinum‐catalyzed hydrosilylation (see below) …”

Section: Piers–rubinsztajn (Pr) Reactionmentioning

confidence: 99%

“…For example, polymers of fluorocarbons and silicones were shown to result from sequential PR reactions and then thermolysis to facilitate 2 + 2c ycloadditions with perfluoroalkenes to give linear or crosslinked polymers ( Figure 9A). [47] Rambarran et al showed that, following the PR reaction,H uisgen or azide/alkyne click reactions could be used to create silicone/PEG (or cyclodextrin) surfactants (Figure 9B), [48] elastomers ( Figure 9C), [49] copolymers [50] or adhesives. [51] The most important orthogonal reaction in silicone systemsisp latinum-catalyzed hydrosilylation (see below).…”

Section: Aroh and Arosimentioning

confidence: 99%

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New Control Over Silicone Synthesis using SiH Chemistry: The Piers–Rubinsztajn Reaction

Brook

2018

Chemistry A European J

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104

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There is a strong imperative to synthesize polymers with highly controlled structures and narrow property ranges. Silicone polymers do not lend themselves to this paradigm because acids or bases lead to siloxane equilibration and loss of structure. By contrast, elegant levels of control are possible when using the Piers-Rubinsztajn reaction and analogues, in which the hydrophobic, strong Lewis acid B(C F ) activates SiH groups, permitting the synthesis of precise siloxanes under mild conditions in high yield; siloxane decomposition processes are slow under these conditions. A broad range of oxygen nucleophiles including alkoxysilanes, silanols, phenols, and aryl alkyl ethers participate in the reaction to create elastomers, foams and green composites, for example, derived from lignin. In addition, the process permits the synthesis of monofunctional dendrons that can be assembled into larger entities including highly branched silicones and dendrimers either using the Piers-Rubinsztajn process alone, or in combination with hydrosilylation or other orthogonal reactions.

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Section: Piers–rubinsztajn (Pr) Reactionmentioning

confidence: 99%

Section: Aroh and Arosimentioning

confidence: 99%

New Control Over Silicone Synthesis using SiH Chemistry: The Piers–Rubinsztajn Reaction

Brook

2018

Chemistry A European J

Self Cite

104

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“…Over the last years, important advances have been made in the field of smart materials, especially for intrinsic self-healing polymer materials, which exploit dynamic bonds, typically generated by supramolecular chemistry approaches, to create self-assembling networks. 1,2 Noncovalent cross-linked systems via supramolecular interactions, such as π-π stacking, [3][4][5] ionic interactions (eg, ionomers), [6][7][8] metal-ligand associations [9][10][11][12] and, in most cases, hydrogen-bonding interactions, [13][14][15][16][17][18][19] have been developed and characterized for this purpose. In some cases, the approach relies on the modification of polymers with functional groups that can interact with each other through explicit strong or weak associations, resulting in the formation of a phase different from the bulk polymer.…”

Section: Introductionmentioning

confidence: 99%

Viscoelastic properties and self‐healing behavior in a family of supramolecular ionic blends from silicone functional oligomers

Suriano

Boumezgane

Tonelli

et al. 2020

Polymers for Advanced Techs

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Supramolecular solid‐like polymer gels were obtained, through acid‐base interactions, starting from highly viscous amino‐terminated and carboxylic‐terminated telechelic PDMS oligomers, with different molecular weights, ranging approximately from 900 to 27 000 g/mol. The obtained blends were studied and characterized in terms of viscoelastic behavior, tensile properties, and self‐healing abilities, with the aim of gaining a better understanding of structure‐property relationships in these supramolecular ionic blends. IR spectroscopy confirmed the formation of supramolecular ionic interactions thanks to the presence of ammonium carboxylate group absorbance. Thermal analysis showed the formation of a crystalline phase at room temperature in some of the supramolecular blends when the molecular weight was lower than 27 000 g/mol. An increase in crystallinity by decreasing the chain length and therefore their molecular weights was also observed. These supramolecular PDMS materials showed self‐healing abilities with a value of healing efficiency ranging from 25% up to 52%. Samples tested with creep recovery analyses showed a viscoelastic behavior. Interpolation of the creep curves according to the four‐parameter Voigt model provides a relationship between the viscoelastic behavior of these PDMS materials and their self‐healing abilities. Our results show how the control of the thermal, viscoelastic, and mechanical properties of these materials allows the design of supramolecular blends based on acid‐base interactions with improved self‐healing properties.

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“…N ‐Methyl‐2‐sulfanylacetamide ( 4 ) was also selected in order to introduce a relatively hydrophilic group able to provide strong hydrogen bonding and to impart solubility to the corresponding grafted polysiloxane in polar solvents, such as DMF or DMSO. Actually, such polysiloxanes soluble in DMF or DMSO are interesting for the preparation of carbohydrate grafted polysiloxanes (‘glycosilicones’), since they would enable the direct grafting of unprotected carbohydrate moieties in monophasic conditions …”

Section: Introductionmentioning

confidence: 99%

“…Actually, such polysiloxanes soluble in DMF or DMSO are interesting for the preparation of carbohydrate grafted polysiloxanes ('glycosilicones'), since they would enable the direct grafting of unprotected carbohydrate moieties in monophasic conditions. [56][57][58] Concerning the gold nanoparticles, the wavelength of the Surface Plasmon resonance (SPR) absorption band is affected by many factors. [59,60] It is mainly affected by the particle shape, [61] dimensions and aggregation.…”

Section: Introductionmentioning

confidence: 99%

Polysiloxanes Modified by Thiol‐Ene Reaction and Their Interaction with Gold Nanoparticles

Lemonier

Marty

Fitremann

2019

Helvetica Chimica Acta

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A poly(vinylmethyl‐co‐dimethyl)siloxane has been functionalized with phenylethanethiol, N‐methylmercaptoacetamide and heptadecafluoro‐1‐decanethiol by a thermal radical thiol‐ene reaction initiated by azobisisobutyronitrile. The resulting polymers were obtained in good yields with most of the time a complete conversion of the vinyl groups. The reaction also preserved the fragile polysiloxane backbone. The polymer, grafted with about 25 % of mercapto‐acetamide groups is soluble in polar solvents such as dimethylformamide and dimethyl sulfoxide, opening the way for further functionalization with polar molecules such as unprotected carbohydrates. Spherical and branched gold nanoparticles were coated with these polymers. This coating induced a surface resonance plasmon shift resulting from the interaction of the grafted polysiloxanes with the nanoparticle surface. The shift can be explained by the variation of the refractive index of the side groups but may be also related to the self‐organization of polysiloxanes and their interactions with the gold surface depending on their polarity.

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Sweet supramolecular elastomers from α,ω-(β-cyclodextrin terminated) PDMS

Cited by 20 publications

References 63 publications

New Control Over Silicone Synthesis using SiH Chemistry: The Piers–Rubinsztajn Reaction

New Control Over Silicone Synthesis using SiH Chemistry: The Piers–Rubinsztajn Reaction

Viscoelastic properties and self‐healing behavior in a family of supramolecular ionic blends from silicone functional oligomers

Polysiloxanes Modified by Thiol‐Ene Reaction and Their Interaction with Gold Nanoparticles

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