Fabrication of Reactive Poly(Phenyl-Substituted Siloxanes/Silsesquioxanes) with Si‒H and Alkoxy Functional Groups via the Piers–Rubinsztajn Reaction

Yi, Minghao; Chen, Xunjun; Wu, Shufang; Ge, Jianfang; Zhou, Xinhua; Yin, Geping

doi:10.3390/polym10091006

Cited by 15 publications

(20 citation statements)

References 34 publications

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“…1 H NMR and 13 C NMR spectra were measured on a Bruker AVANCE-300 or 400 NMR spectrometer (Karlsruhe, Germany), with CDCl 3 as the solvent. Quantitative 29 Si NMR spectroscopy (Karlsruhe, Germany) was performed using an inverse gated 1 H-decoupling sequence. Samples were prepared in Cr(acac) 3 /CDCl 3 solution (0.1 M Cr(acac) 3 ).…”

Section: Materials and Characterizationmentioning

confidence: 99%

“…The Si-H containing monomers, M-1 to M-3, were synthesized following the literature procedures [17,38]. Their structures were characterized by 1 H NMR, 13 C NMR, and 29 Si NMR and the satisfactory analysis data were obtained.…”

Section: Synthesismentioning

confidence: 99%

“…The structures of all the polymers were fully determined by FT-IR, 1 H NMR, 13 C NMR, 29 Si NMR, and elemental analysis. The FT-IR spectra of these polymers were shown in Figure 1 and Figure S1 (Supplementary Materials).…”

Section: Characterizationmentioning

confidence: 99%

“…Herein, we present a series of novel hyperbranched polycarbosiloxanes, Si-HBP-1 to Si-HBP-3, based on methyl-, or phenyl-triethoxylsilane and three Si-H containing aromatic monomers, including 1,4-bis(dimethylsilyl)benzene (M-1), 4,4 -bis(dimethylsilyl)-1,1 -biphenyl (M-2) and 1,1 -bis(dimethylsilyl) ferrocene (M-3), in the presence of B(C 6 F 5 ) 3 as the catalyst by the P-R reactions (Scheme 1). The obtained Si-HBPs were fully characterized by Fourier transform infrared spectroscopy (FT-IR), 1 H NMR, 13 C NMR, 29 Si NMR and gel permeation chromatography (GPC). Moreover, the pyrolysis of ferrocene-based polycarbosiloxanes at elevated temperatures can afford novel nanostructured ceramics with good magnetizability in a high yield.…”

Section: Introductionmentioning

confidence: 99%

“…In particular, developing Si-HBPs via simple, rapid and mild synthetic procedures is highly desirable. The Piers-Rubinsztajn (P-R) reaction, namely the condensation of alkoxysilanes with hydrosilanes, has rapidly developed since it was found in the 1990s [22,23], because this strategy is mild and provides a possibility for the controlled or precise synthesis of silicones, including small molecules, linear polymers, and crosslinked materials [24][25][26][27][28][29][30][31]. For example, the P-R coupling reactions of various organic tris(dimethylsiloxy)silane and trialkoxysilane compounds can generate a series of cyclic polysiloxanes with cyclotetrasiloxane subunits in a simple one-step synthesis [32].…”

Section: Introductionmentioning

confidence: 99%

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Hyperbranched Polycarbosiloxanes: Synthesis by Piers-Rubinsztajn Reaction and Application as Precursors to Magnetoceramics

Zhang

Xue

et al. 2020

Polymers

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Silicon-containing hyperbranched polymers (Si-HBPs) have drawn much attention due to their promising applications. However, the construction of Si-HBPs, especially those containing functional aromatic units in the branched backbones by the simple and efficient Piers-Rubinsztajn (P-R) reaction, has been rarely developed. Herein, a series of novel hyperbranched polycarbosiloxanes were prepared by the P-R reactions of methyl-, or phenyl-triethoxylsilane and three Si-H containing aromatic monomers, including 1,4-bis(dimethylsilyl)benzene, 4,4 -bis(dimethylsilyl)-1,1 -biphenyl and 1,1 -bis(dimethylsilyl)ferrocene, using B(C 6 F 5 ) 3 as the catalyst for 0.5 h at room temperature. Their structures were fully characterized by Fourier transform infrared spectroscopy, 1 H NMR, 13 C NMR, and 29 Si NMR. The molecular weights were determined by gel permeation chromatography. The degrees of branching of these polymers were 0.69-0.89, which were calculated based on the quantitative 29 Si NMR spectroscopy. For applications, the ferrocene-linked Si-HBP can be used as precursors to produce functional ceramics with good magnetizability after pyrolysis at elevated temperature.

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Section: Materials and Characterizationmentioning

confidence: 99%

Section: Synthesismentioning

confidence: 99%

Section: Characterizationmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

See 3 more Smart Citations

Hyperbranched Polycarbosiloxanes: Synthesis by Piers-Rubinsztajn Reaction and Application as Precursors to Magnetoceramics

Zhang

Xue

et al. 2020

Polymers

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High‐Throughput Synthesis and Characterization of Aryl Silicones by Using the Piers–Rubinsztajn Reaction

Schneider

Brook

2019

Chemistry A European J

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Arylsilicones are widely exploited for their thermal and optical properties. The creation of phenylsilicone elastomers with specific physical properties is typically done by a “one‐off” formulation and test process. Herein, it is demonstrated that high‐throughput synthesis methods can be used to rapidly prepare a series of arylsilicone elastomers and then the relative impact of different aryl groups on their physical properties is assessed. Aromatic groups were incorporated into polydimethylsiloxane (PDMS) elastomers by exploiting the relative reactivity of different functional groups in the Piers–Rubinsztajn reaction. To analyze trends in the silicone mechanical properties as a function of increasing aryl concentration—structure/property relationships—libraries of elastomers were both quickly synthesized and characterized by using high‐throughput suites starting from low viscosity silicone oils/monomers in 96‐well plates. Liquid handling parameters were optimized to effectively work with the silicones. Incorporating aryl instead of alkyl crosslinkers into the PDMS backbone increased the silicone elastomer modulus by approximately 50 % (at a crosslink density of 6 %); elastomers prepared with an aromatic crosslinker with three contact points led to much higher moduli compared with those with one contact point at the same crosslink density. When located at precise rather than random points on the silicone chains, diphenylsilicones had lower moduli than analogous monophenylsilicones.

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Facile synthesis of phenyl‐rich functional siloxanes from simple silanes

Schneider

et al. 2020

Journal of Polymer Science

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Phenyl-rich silicone polymers are used for their excellent thermal properties and high refractive indices. Traditional syntheses of these polymers utilize cationic or anionic equilibration, which limits the molecular weights that can be achieved due, in part, to the coproduction of cyclic monomers that must be removed. Kinetically controlled processes may reduce the impact of these limitations, but require high temperatures, alkyllithium initiators and an inert atmosphere; precise structures are difficult to access. The Piers-Rubinsztajn reaction, combined with hydrolysis, allows the synthesis of highly ordered, Si-H terminated, phenyl-rich silicone homo-and copolymers comprised of phenylmethyl, diphenyl and, dimethylsilicone monomers. The processes are mild and permit a high level of structural control, including alternating copolymers with different levels of phenyl content (Ph/Si = 0.3-1.5) with molecular weights up to 100 kDa. Yet higher molecular weights could be achieved-M n up to 300 kDa-when phenyl-rich siloxanes were incorporated into block copolymers with dimethylsilicones (Ph/Si = 0.4). Unlike kinetic processes in which cyclic byproducts are formed by redistribution or backbiting (particularly at high conversion), in this process cyclics form near the onset of the reaction and only with low molecular weight starting materials (< 4 siloxane units).

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Fabrication of Reactive Poly(Phenyl-Substituted Siloxanes/Silsesquioxanes) with Si‒H and Alkoxy Functional Groups via the Piers–Rubinsztajn Reaction

Cited by 15 publications

References 34 publications

Hyperbranched Polycarbosiloxanes: Synthesis by Piers-Rubinsztajn Reaction and Application as Precursors to Magnetoceramics

Hyperbranched Polycarbosiloxanes: Synthesis by Piers-Rubinsztajn Reaction and Application as Precursors to Magnetoceramics

High‐Throughput Synthesis and Characterization of Aryl Silicones by Using the Piers–Rubinsztajn Reaction

Facile synthesis of phenyl‐rich functional siloxanes from simple silanes

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