Synthesis and Characterization of Polyhedral Oligomeric Silsequioxane-Core Star Polystyrene via Nitroxide-Mediated Polymerization

Glé, David; Phan, Trang N. T.; Monier, Valérie; Charles, Laurence; Gigmès, Didier

doi:10.1021/bk-2012-1101.ch010

Cited by 3 publications

(3 citation statements)

References 37 publications

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“…Octafunctional POSS nanocages have also been employed as multifunctional NMP/ATRP initiators to afford star‐like hybrid polymers . Hussain et al converted octa(aminophenyl)silsesquioxane (POSS(NH 2 ) 8 ) and octafunctional octakis(3‐hydroxypropyldimethylsiloxy)octasilsesquioxane (POSS(OH) 8 ) nanocages into ATRP octafunctional initiators (Scheme (f) and (g)) by reacting with 2‐bromoisobutyryl bromide to prepare, via ATRP, hybrid star PMMA with POSS as core and PMMA chains forming the arms.…”

Section: Hybrid Star Polymersmentioning

confidence: 99%

Recent developments in nanostructured polyhedral oligomeric silsesquioxane‐based materials via ‘controlled’ radical polymerization

Hussain

Shah

2014

Polymer International

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Polyhedral oligomeric silsesquioxane (POSS) compounds consist of unique three-dimensional nanocages with a general composition of (RSiO 1.5 ) n , where R groups are organic moieties for enhanced physical and chemical compatibility of inorganic POSS frameworks with organic systems. Due to their unique size, structure and properties there has been tremendous progress over the last decade or so in the chemistry and applications of POSSs in various fields of materials, nanoscience and nanotechnology. Advances in synthetic polymer chemistry, particularly the advent of 'controlled' radical polymerization (CRP), namely atom transfer radical polymerization, reversible addition-fragmentation chain transfer and nitroxide-mediated polymerization, have enabled polymer chemists to integrate inorganic POSS nanocages into welldefined copolymers of almost any architecture, thus generating nanostructured materials with controlled molar masses and compositions, and well-defined and tunable morphologies. Thus, these new strategies of employing POSS nanocages in polymer chemistry could lead to potential new applications in various areas of nanoscience and nanotechnology. The present paper covers recent trends and developments over the last five years or so in POSS-based nanostructured materials via CRP. Also included is the combined CRP and 'click' chemistry approach to achieve POSS-containing well-defined hybrid copolymers.

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Section: Hybrid Star Polymersmentioning

confidence: 99%

Recent developments in nanostructured polyhedral oligomeric silsesquioxane‐based materials via ‘controlled’ radical polymerization

Hussain

Shah

2014

Polymer International

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“…Octakis(3-ammoniumpropyl)octasilsesquioxane octachloride (POSS-NH 2 •HCl) was synthesized according to the published procedure. 41 Potassium vinyl sulfonyl(trifluoromethane sulfonyl)imide (vinyl-KTFSI) was prepared as described in our previous work. 42 All solvents and other reagents were synthesis grade and were used without further purification.…”

Section: ■ Introductionmentioning

confidence: 99%

Polyhedral Oligomeric Silsesquioxane-Based Macroanions to Level Up the Li⁺ Transport Number of Electrolytes for Lithium Batteries

et al. 2022

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Increasing the lithium transport number in liquid and polymer electrolytes is an important task for higher power performance since it limits the promotion of concentration gradient and mitigation of dendrite nucleation. One promising route to limit anion mobility is the design of macroanions. In this paper, by varying the number of lithium bis(trifluoromethane)sulfonimide (LiTFSI) salt and poly(ethylene glycol) (PEG) chains attached to polyhedral oligomeric silsesquioxane (POSS) nanoparticles, a series of POSS-based macroanions were synthesized and complexed with the tetraglyme (TEG) model solvent to form electrolytes at different concentrations of EO/Li from 10 to 25. While a high transport number between 0.7 and 0.86 was obtained as expected, a significantly lower cationic conductivity was observed compared to the TEG-LiTFSI reference electrolyte at the same lithium concentration. An understanding of this behavior is necessary for the design of next-generation electrolytes. Thus, a complete study coupling morphologic (small-angle X-ray scattering, SAXS), thermal (differential scanning calorimetry/thermogravimetric analysis, DSC/TGA), conductivity (electrochemical impedance spectroscopy, EIS), and 1 H, 7 Li, and 19 F diffusion nuclear magnetic resonance (NMR) analyses is provided to establish in a single equation (eq 11) the relationship between the Li + ionic transport properties and the size of macroanions. These latter impact strongly the transport number but also the electrolyte bulk properties, such as the viscosity and the tortuosity induced by the large POSS inorganic cores. In addition, it is shown that the chemical affinity of the organic POSS shell and the solvent drives the Li + dissociation rate and thus the content of free Li + ions. These results provide a deep insight into the intricacy of the physical properties (eq 11) that leads to high cationic conductivity, which can be a helpful intellectual platform for the target design of new macroanions.

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“…[16,17] Despite the innumerable procedures and known alkoxyamines, very few examples of multifunctional alkoxyamines have been reported. [18][19][20][21] This is remarkable since such multifunctional alkoxyamines allow the generation of star-shaped polymers with a defined center and thereby a fixed number of arms, which find application as viscosity improvers, organic nanoparticles, and drug delivery systems. [22][23][24][25] Alkoxyamines can also be used as building blocks in the nitroxide exchange reaction (NER).…”

Section: Introductionmentioning

confidence: 99%

Rigid Multidimensional Alkoxyamines: A Versatile Building Block Library

et al. 2020

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Since the discovery of the "living" free-radical polymerization, alkoxyamines were widely used in nitroxide-mediated polymerization (NMP). Most of the known alkoxyamines bear just one functionality with only a few exceptions bearing two or more alkoxyamine units. Herein, we present a library of novel multidimensional alkoxyamines based on commercially available, rigid, aromatic core structures. A versatile approach allows the introduction of different sidechains which have an impact on the steric hindrance and dissociation behavior of the alkoxyamines. The reaction to the alkoxyamines was optimized by implementing a mild and reliable procedure to give all target compounds in high yields. Utilization of biphenyl, pterphenyl, 1,3,5-triphenylbenzene, tetraphenylethylene, and tetraphenyl-methane results in linear, trigonal, square planar, and tetrahedral shaped alkoxyamines. These building blocks are useful initiators for multifold NMP leading to star-shaped polymers or as a linker for the nitroxide exchange reaction (NER), to obtain dynamic frameworks with a tunable crosslinking degree and self-healing abilities.

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Synthesis and Characterization of Polyhedral Oligomeric Silsequioxane-Core Star Polystyrene via Nitroxide-Mediated Polymerization

Cited by 3 publications

References 37 publications

Recent developments in nanostructured polyhedral oligomeric silsesquioxane‐based materials via ‘controlled’ radical polymerization

Recent developments in nanostructured polyhedral oligomeric silsesquioxane‐based materials via ‘controlled’ radical polymerization

Polyhedral Oligomeric Silsesquioxane-Based Macroanions to Level Up the Li⁺ Transport Number of Electrolytes for Lithium Batteries

Rigid Multidimensional Alkoxyamines: A Versatile Building Block Library

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Synthesis and Characterization of Polyhedral Oligomeric Silsequioxane-Core Star Polystyrene via Nitroxide-Mediated Polymerization

Cited by 3 publications

References 37 publications

Recent developments in nanostructured polyhedral oligomeric silsesquioxane‐based materials via ‘controlled’ radical polymerization

Recent developments in nanostructured polyhedral oligomeric silsesquioxane‐based materials via ‘controlled’ radical polymerization

Polyhedral Oligomeric Silsesquioxane-Based Macroanions to Level Up the Li+ Transport Number of Electrolytes for Lithium Batteries

Rigid Multidimensional Alkoxyamines: A Versatile Building Block Library

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Polyhedral Oligomeric Silsesquioxane-Based Macroanions to Level Up the Li⁺ Transport Number of Electrolytes for Lithium Batteries