Organocatalytic controlled/living ring-opening polymerization of cyclotrisiloxanes initiated by water with strong organic base catalysts

Fuchise, Keita; Igarashi, Masayasu; Satō, Kazuhiko; Shimada, Shigeru

doi:10.1039/c7sc04234e

Cited by 65 publications

(94 citation statements)

References 60 publications

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“…By using the model of end group analysis, we compare the signal for the CH 3 -group of the initiator NeOH with the signal of the Si-CH 3 group assuming that every polymer chain possesses the same initiating group. The high M n,NMR indicates the presence of macrocycles or another initiator, possibly due to water residues in the P 2 -t-Bu solution, as water in combination with strong bases is known to initiate the ROP of cyclosiloxane [36,38]. Consequently, the study focuses on the employment of P 4 -t-Bu as a catalyst in the following.…”

Section: Molar Mass Controlmentioning

confidence: 99%

“…Usually, alkali metal hydroxides such as KOH, alcoholates, silonates or lithium organyls are used as initiators/catalysts. It is well known that, this way, high-molecular polymers with excellent end group control are accessible [31,36,37]. The polymerization rate strongly depends on the size of the cation [21,26].…”

Section: Introductionmentioning

confidence: 99%

“…The polymerization rate strongly depends on the size of the cation [21,26]. However, the use of these initiators/catalysts involves problems like low solubility, long reaction times and the requirement for high temperatures [36,38]. Molenberg et al [39,40] reported a fast and effective catalytic system for these monomers using the organophilic phosphazene bases developed by Schwesinger and Schlemper [41,42] as catalysts.…”

Section: Introductionmentioning

confidence: 99%

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Creation of a PDMS Polymer Brush on SiO2-Based Nanoparticles by Surface-Initiated Ring-Opening Polymerization

et al. 2020

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The incorporation of nanoparticles into soft matrices opens a broad spectrum of novel property combinations. However, one of the major challenges for these systems remains the compatibilization of particles with the surrounding matrix by proper surface functionalization. For silicon-based systems or liquid crystalline phases, polydimethylsiloxane (PDMS) brushes at the surface of particles increase the stability against particle agglomeration in such systems. Here, we report a novel approach for the functionalization of particles with a polysiloxane brush by surface-initiated ring-opening polymerization of a cyclosiloxane. For this purpose, surface hydroxy groups of silica and silica-coated hematite particles are used as initiators in combination with phosphazene bases as catalysts. The ring–chain equilibrium of a model-based solution polymerization is investigated in detail to find the appropriate reaction parameters. The corresponding molar masses are determined and compared by 1H-NMR and SEC measurements to confirm the underlying mechanism. In the resulting hybrid nanostructures, a covalently bound PDMS fraction is achieved up to 47 mass %.

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Section: Molar Mass Controlmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Creation of a PDMS Polymer Brush on SiO2-Based Nanoparticles by Surface-Initiated Ring-Opening Polymerization

et al. 2020

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“…[36] Polykondensationsreaktionen,d ie neue Reaktionswege und ausgefeilte Sequenzkontrolle bieten, werden ebenfalls gesucht. So konnten beispielsweise starke organische Basen, insbesondere Guanidine,d ie lebende ROPv on Cyclooligosiloxanen mit Wasser als Initiator katalysieren und Polymere mit engen Dispersitäten von < 1.2, hohen M n -Werten und Umsätzen sowie hoher Genauigkeit bei der Endgruppenschützenden Funktionalisierung liefern (25;S chema 4a).…”

Section: Polysiloxaneunclassified

“…So konnten beispielsweise starke organische Basen, insbesondere Guanidine,d ie lebende ROPv on Cyclooligosiloxanen mit Wasser als Initiator katalysieren und Polymere mit engen Dispersitäten von < 1.2, hohen M n -Werten und Umsätzen sowie hoher Genauigkeit bei der Endgruppenschützenden Funktionalisierung liefern (25;S chema 4a). [36] Polykondensationsreaktionen,d ie neue Reaktionswege und ausgefeilte Sequenzkontrolle bieten, werden ebenfalls gesucht. In diesem Zusammenhang zeichnet sich B(C 6 F 5 ) 3 als leistungsfähiger Organokatalysator aus.…”

Section: Polysiloxaneunclassified

Funktionelle polymere Materialien auf der Basis von Hauptgruppen‐Elementen

Vidal

Jäkle

2019

Angewandte Chemie

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In den letzten zehn Jahren wurden enorme Fortschritte bei der Synthese von Polymeren erzielt, die Hauptgruppen‐Elemente enthalten und über die typischen organischen Polymere hinausgehen. Einzigartige Eigenschaften, die sich aus drastischen Unterschieden in Bindung und molekularer Geometrie, elektronischer Struktur und chemischer Reaktivität ergeben, werden in den unterschiedlichsten Anwendungsbereichen genutzt. In dem Aufsatz werden die jüngsten Fortschritte bei Polymeren mit anorganischem Rückgrat hervorgehoben, es wird diskutiert, wie die Lewis‐Säure/Base‐Funktionalisierung von Polymeren zu beispielloser Reaktivität führt, und es werden konjugierte Hybride mit spezifischen elektronischen Strukturen für die Sensorik sowie Anwendungen in Organische‐Elektronik‐Geräten vorgestellt.

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Ionic and Coordination Ring‐Opening Polymerization

Penczek¹,

Biela²,

Cypryk³

et al. 2022

Macromolecular Engineering

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This article provides the up‐to‐date and comprehensive review (over 700 citations) of all the important subjects of the ring‐opening polymerization (ROP) methods of polymers syntheses. This is the method of synthesis of several important classes of polymers that cannot be prepared in a different way (e.g., polyethers). It also complements known methods of polycondensation and ROP often is the method of choice. ROP is particularly important in syntheses of the biodegradable polymers‐polylactide and poly(ε‐caprolactone), discussed in details. Applications of these polymers, as well as polysiloxanes in biomedical applications are irreplaceable in the modern medicine. Either as bulk polymers or as nano‐ and microspheres, described In this article separately. There are sections in the present version that were not presented in the previous editions. This is description of polyoxazolines, polymers with phosphorus atoms in the chains, as well as mentioned above polysiloxanes an microspheres. We introduced also section describing novel analytical methods, particularly useful in studies of polymers with various architectures (star shape, multibranched etc.). Besides the synthetic aspects of ROP, this article describes thermodynamics and kinetic features of the living/controlled polymerizations, particularly by activated monomer mechanism and importance of dormant polymers in precision syntheses of desired structures.

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Organocatalytic controlled/living ring-opening polymerization of cyclotrisiloxanes initiated by water with strong organic base catalysts

Abstract: Organocatalytic controlled/living ring-opening polymerization of cyclotrisiloxanes using water as an initiator and strong organic bases as catalysts produced a variety of linear polysiloxanes with narrow polydispersity and well-defined symmetric structures.

Cited by 65 publications

References 60 publications

Creation of a PDMS Polymer Brush on SiO2-Based Nanoparticles by Surface-Initiated Ring-Opening Polymerization

Creation of a PDMS Polymer Brush on SiO2-Based Nanoparticles by Surface-Initiated Ring-Opening Polymerization

Funktionelle polymere Materialien auf der Basis von Hauptgruppen‐Elementen

Ionic and Coordination Ring‐Opening Polymerization

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