Functionalization-induced self-assembly under ambient conditions <i>via</i> thiol-epoxide “click” chemistry

Howe, David H.; Jenewein, Ken J.; Hart, James L.; Taheri, Mitra L.; Magenau, Andrew J. D.

doi:10.1039/c9py01144g

Cited by 16 publications

(15 citation statements)

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“…While surface modification is critical for well-dispersed nanocomposites and nanofiller compatibility, the underlying polymerization reaction must also be tolerant to the presence of filler and highly efficient to ensure proper network formation. Click chemistries, first described in 2001, are a family of reactions that have been identified as a powerful and enabling tool for the synthesis of polymer materials because they are rapid, orthogonal, simple to perform, and proceed to quantitative conversions with few or little byproducts. − The thiol-isocyanate “click” reaction has proven to be particularly useful in polymer synthesis, offering flexibility and simplicity for polymer chain extensions, , chain-end modifications, , side group modifications, and production of thiourethane polymer networks for encapsulation and optical materials . Thiourethane polymers produced via the thiol-isocyanate “click” reaction also share many desirable characteristics with the more common polyurethane (hydrogen bonding, elasticity, and impact resistance), with the additional advantages of adhering to many “click” chemistry attributes including extremely rapid reaction rates (comparable to amine–isocyanate reactions), high network uniformity, high monomer conversion, and few or no byproducts produced by the reaction .…”

Section: Introductionmentioning

confidence: 99%

Well-Dispersed Nanocomposites Using Covalently Modified, Multilayer, 2D Titanium Carbide (MXene) and In-Situ “Click” Polymerization

et al. 2021

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Despite the excellent mechanical and electrical performance of MXene−polymer nanocomposites, methods for producing these materials on a larger scale are limited by low-yielding, delaminated, MXene suspensions that are typically employed for their synthesis. Moreover, the hydrophilicity of MXenes restricts the production of well-dispersed nanocomposites with many polymer matrices. In this contribution, we address such limitations and report, for the first time, a simple method to covalently modify multilayered Ti 3 C 2 T z MXenes with isocyanates, which enables their successful dispersion within a hydrophobic thiourethane matrix. The efficacy of our covalent modification was determined to yield high levels of surface grafts and suggests quantitative conversion of the oxygen-containing terminations. In situ-polymerized thiourethane "click" matrices were used to demonstrate the utility of this modification for accessing well-dispersed nanocomposites under ambient conditions. The ease of producing modified, multilayered, MXenes at scale and the availability of a wide variety of isocyanates render this method scalable and highly modular. Furthermore, the reported isocyanate treatment was found to be a valuable tool for easily quantifying the concentration of reactive (oxygen-containing) terminations on MXene surfaces.

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Section: Introductionmentioning

confidence: 99%

Well-Dispersed Nanocomposites Using Covalently Modified, Multilayer, 2D Titanium Carbide (MXene) and In-Situ “Click” Polymerization

et al. 2021

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“…Beyond trapping the fluctuating disordered state or driving nanostructural changes in linear block polymers, in situ chemical transformation to convert linear polymers into topologically complex macromolecules is only starting to be exploited in materials design. ,− The self-assembly of polymers with nonlinear architectures such as graft, − miktoarm star, − and comb–coil − has opened exciting possibilities for creating unconventional nanoscale morphologies. Similar to linear block polymers, the morphology of block polymers with nonlinear architectures is dependent on N , f , and χ, but is additionally contingent upon the location and the number of polymer blocks. − By leveraging orthogonal control over the chemistry of the comb and coil blocks, a myriad of different mesophases are accessible, including complex phases such as the parallel and perpendicular lamella-in-lamella, spheres-in-lamella, hexagonally perforated lamellae (HPL), and lamella-in-cylinders. − In many of these cases, the synthetic procedures for creating complex molecular architectures are demanding.…”

Section: Introductionmentioning

confidence: 99%

Deciphering the Complex Phase Behavior during Polymerization-Induced Nanostructural Transitions of a Block Polymer/Monomer Blend

et al. 2020

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The simultaneous use of nonequilibrium reaction processing and complex macromolecular architecture is an exciting way to achieve nanostructures that are not easily accessible via standard static block polymer self-assembly. Previous work has shown that the polymerization of styrene in the presence of a poly(styrene)-block-poly(butadiene) (PS-PBD) diblock copolymer induces a nanostructural transition from a lamellar (LAM) to a hexagonally packed cylinder (HEX) morphology. The transition was found to be driven by in situ PS grafting from the PBD block, which transforms the PS-PBD coil−coil diblock copolymer to a poly(styrene)-block-[poly(butadiene)-graf t-poly(styrene)] (PS-b-PBD-g-PS) coil−comb block polymer. In situ small-angle X-ray scattering and oscillatory shear dynamic mechanical spectroscopy measurements show that the order−order transition is not a simple epitaxial transition seen in prototypical block polymers, but undergoes a complex phase path in which the starting LAM phase at room temperature before polymerization initially disorders at elevated temperatures, evolves from a disordered phase to what is presumed to be a hexagonally perforated lamellae phase during the polymerization, and then transitions to a HEX phase on cooling to room temperature. The high-temperature phase persists for extended periods of time during the polymerization process, which allows for both the trapping and the characterization of the structure at room temperature. By utilizing nonequilibrium reactive processing to convert linear block copolymers to comb−coil type polymers, the creation of polymers with complex molecular topologies can be synthetically simplified while simultaneously allowing for the development of new processing modalities.

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“…Thiol-based reactions are the most popular click chemistry methodology applied to rubbers and comprise a family of reactions like the thiol-ene, [96] thiol-yne, [119,120] thiol-halogen, [121] thiol-epoxy, [122][123][124][125] thiol-isocyanate, [126] which are often described as thiol-X reactions. Thiol additions can also proceed through Michael additions in the presence of catalyst.…”

Section: Rubber Modifications Via Thiol-x Reactionsmentioning

confidence: 99%

Enzymatic and Chemical Approaches for Post‐Polymerization Modifications of Diene Rubbers: Current state and Perspectives

Soares

Steinbüchel

2021

Macromolecular Bioscience

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Diene rubbers are polymeric materials which present elastic properties and have double bonds in the macromolecular backbone after the polymerization process. Post-polymerization modifications of rubbers can be conducted by enzymatic or chemical methods. Enzymes are environmentally friendly catalysts and with the increasing demand for rubber waste management, biodegradation and biomodifications have become hot topics of research. Some rubbers are renewable materials and are a source of organic molecules, and biodegradation can be conducted to obtain either oligomers or monomers. On the other hand, chemical modifications of rubbers by click-chemistry are important strategies for the creation and combination of new materials. In a way to expand the scope of uses to other non-traditional applications, several and effective modifications can be conducted with diene rubbers. Two groups of efficient tools, enzymatic, and chemical modifications in diene rubbers, are summarized in this review. By analyzing stereochemical and reactivity aspects, the authors also point to some applications perspectives for biodegradation products and to rational modifications of diene rubbers by combining both methodologies.

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Functionalization-induced self-assembly under ambient conditions via thiol-epoxide “click” chemistry

Abstract: Polymer micelles were formed using thiol-epoxide “click” chemistry to trigger functionalization-induced self-assembly (FISA) of block copolymers by modifying a reactive glycidyl methacrylate block with solvophobes.

Cited by 16 publications

References 50 publications

Well-Dispersed Nanocomposites Using Covalently Modified, Multilayer, 2D Titanium Carbide (MXene) and In-Situ “Click” Polymerization

Well-Dispersed Nanocomposites Using Covalently Modified, Multilayer, 2D Titanium Carbide (MXene) and In-Situ “Click” Polymerization

Deciphering the Complex Phase Behavior during Polymerization-Induced Nanostructural Transitions of a Block Polymer/Monomer Blend

Enzymatic and Chemical Approaches for Post‐Polymerization Modifications of Diene Rubbers: Current state and Perspectives

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