Polymerization of epoxide monomers promoted by <i>t</i>BuP<sub>4</sub> phosphazene base: a comparative study of kinetic behavior

Puchelle, Valentin; Du, Haiqin; Illy, Nicolas; Guégan, Philippe

doi:10.1039/d0py00437e

Cited by 14 publications

(13 citation statements)

References 44 publications

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“…1) [16]. On the other hand, higher alkylene oxides, such as butylene oxide (M3) and octylene oxide (M4), can be polymerized using t-Bu-P 4 virtually without side reactions, producing the corresponding well-defined polyethers with narrow dispersity and predictable molecular weights [16,21,24]. A detailed study using M3 revealed the living nature of this polymerization system.…”

Section: Fundamental Aspects and Applicable Monomer Scope Of T-bu-p4-catalyzed Aropmentioning

confidence: 99%

“…Applicable epoxide monomers for t-Bu-P 4 -catalyzed AROP include alkylene oxides (e.g., butylene oxide) [16,21], styrene oxide [22], glycidyl ethers (e.g., benzyl glycidyl ether) [16,21], and glycidyl amines (e.g., dibenzyl glycidyl amine) [23]. The scope and limitations of the present polymerization system are summarized in Fig.…”

Section: Fundamental Aspects and Applicable Monomer Scope Of T-bu-p4-catalyzed Aropmentioning

confidence: 99%

“…2, t-Bu-P 4 has been utilized for the AROP of glycidyl ethers bearing various side chains to produce side-chain-functionalized polyethers with desirable end groups, narrow dispersities, and predicted molecular weights. Among them, OH-protected glycidyl ethers, such as 1-ethoxy ethyl glycidyl ether (M6) [16,21,25], benzyl glycidyl ether (M7) [16], tert-butyl glycidyl ether (M8) [16,21], tetrahydrofuranyl glycidyl ether (M9) [26], and tetrahydropyranyl glycidyl ether (M10) [27], are particularly interesting because their deprotection reaction yields linear polyglycidols. However, the chain transfer reaction has been found to occur in the t-Bu-P 4 -catalyzed AROP of M6 [16,21].…”

Section: Fundamental Aspects and Applicable Monomer Scope Of T-bu-p4-catalyzed Aropmentioning

confidence: 99%

“…Among them, OH-protected glycidyl ethers, such as 1-ethoxy ethyl glycidyl ether (M6) [16,21,25], benzyl glycidyl ether (M7) [16], tert-butyl glycidyl ether (M8) [16,21], tetrahydrofuranyl glycidyl ether (M9) [26], and tetrahydropyranyl glycidyl ether (M10) [27], are particularly interesting because their deprotection reaction yields linear polyglycidols. However, the chain transfer reaction has been found to occur in the t-Bu-P 4 -catalyzed AROP of M6 [16,21]. In contrast, the AROP of M7 proceeded cleanly without side reactions, producing well-defined poly(benzyl glycidyl ether).…”

Section: Fundamental Aspects and Applicable Monomer Scope Of T-bu-p4-catalyzed Aropmentioning

confidence: 99%

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Synthesis of functional and architectural polyethers via the anionic ring-opening polymerization of epoxide monomers using a phosphazene base catalyst

Isono

2021

Polym J

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This focused review provides an overview of our recent work and related research regarding the precise anionic ring-opening polymerization (AROP) of substituted epoxides, including alkylene oxides, glycidyl ethers, and glycidyl amines, using t-Bu-P 4 as the phosphazene base catalyst to produce functional polyethers, such as homopolymers, block copolymers (BCPs), and topologically unique polymers. First, the fundamental aspects and applicable monomer scope of t-Bu-P 4 -catalyzed AROP are discussed. Subsequently, the applications of well-defined polyethers prepared via t-Bu-P 4 -catalyzed AROP to develop functional materials, such as thermoresponsive polymers and Li + conducting polymers, are discussed. Finally, the utility of t-Bu-P 4catalyzed AROP in the precise synthesis of star-shaped, cyclic, and multicyclic polymers is presented. Overall, we intend to illustrate the exploitable utility of the present polymerization system for fundamental and advanced polymer research.

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Section: Fundamental Aspects and Applicable Monomer Scope Of T-bu-p4-catalyzed Aropmentioning

confidence: 99%

Section: Fundamental Aspects and Applicable Monomer Scope Of T-bu-p4-catalyzed Aropmentioning

confidence: 99%

Section: Fundamental Aspects and Applicable Monomer Scope Of T-bu-p4-catalyzed Aropmentioning

confidence: 99%

Section: Fundamental Aspects and Applicable Monomer Scope Of T-bu-p4-catalyzed Aropmentioning

confidence: 99%

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Synthesis of functional and architectural polyethers via the anionic ring-opening polymerization of epoxide monomers using a phosphazene base catalyst

Isono

2021

Polym J

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“…Organic superbase based on phosphazene can also provide an alternative means of synthesizing polyethers. [ 27,41,42 ] Due to the significant size and charge separation of the countercation, they can effectively act as bases rather than nucleophiles, thereby preventing other side reactions. However, the relatively lower basicity of the phosphazene family compared to metal hydroxides makes them useful in only limited cases such as polymerization using epoxide as a monomer.…”

Section: Overviewmentioning

confidence: 99%

Acetal‐Based Functional Epoxide Monomers: Polymerizations and Applications

Baek

Kim

Park

et al. 2021

Macromolecular Bioscience

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Protecting group chemistry is essential for various organic transformation and polymerization processes. In particular, conventional anionic ring‐opening polymerization (AROP) often requires proper protecting group chemistry because it is typically incompatible with most functional groups due to the highly basic and nucleophilic conditions. In this context, many functional epoxide monomers with proper protecting groups are developed, including the acetal group as a representative example. Since the early introduction of ethoxyethyl glycidyl ether, there is significant development of acetal‐based monomers in the polyethers. These monomers are now utilized not only as protecting groups for hydroxyl groups under AROP conditions but also as pH‐responsive moieties for biomedical applications, further expanding their utility in the use of functionalized polyethers. Recent progress in this field is outlined from their synthesis, polymerization, and biomedical applications.

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Simple/Commercially Available Lewis Acid in Anionic Ring‐Opening Polymerization: Powerful Compounds with Multiple Applications in Macromolecular Engineering

Illy,

Fu,

Mongkhoun

2024

ChemCatChem

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Simple and commercially‐available Lewis acids (LA) are commonly used catalysts in anionic ring‐opening polymerization (AROP) reactions. In particular, for the AROP of epoxides, the addition of a Lewis acid allows the transition from a so‐called end‐chain mechanism to a monomer‐activated mechanism. The presence of the LA simultaneously leads to a decrease in the reactivity of active centers through the formation of a three‐species ate complex and to the activation of the monomer by LA coordination to the oxygen atom of the oxirane ring. These two effects result in both an increase in propagation kinetics and a decrease in transfer reactions, which has enabled the synthesis of high molecular weight polyethers. However, the impact of Lewis acids goes far beyond these classic effects. They have indeed enabled the polymerization of new functional monomers as well as the synthesis of heterotelechelic macromolecules. Also widely used as catalysts in copolymerization reactions (statistical, sequential, or alternating) Lewis acids can strongly influence the composition and sequence of monomer units in macromolecules. Finally, Lewis acids can also significantly influence the architecture of the obtained macromolecules. This review aims to list the various contributions of Lewis acids to macromolecular engineering and illustrate them with well‐chosen examples.

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Polymerization of epoxide monomers promoted by tBuP₄ phosphazene base: a comparative study of kinetic behavior

Abstract: This contribution fills the need for quantitative mechanistic and kinetic information for epoxide polymerizations catalyzed by tBuP4 phosphazene base.

Cited by 14 publications

References 44 publications

Synthesis of functional and architectural polyethers via the anionic ring-opening polymerization of epoxide monomers using a phosphazene base catalyst

Synthesis of functional and architectural polyethers via the anionic ring-opening polymerization of epoxide monomers using a phosphazene base catalyst

Acetal‐Based Functional Epoxide Monomers: Polymerizations and Applications

Simple/Commercially Available Lewis Acid in Anionic Ring‐Opening Polymerization: Powerful Compounds with Multiple Applications in Macromolecular Engineering

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Polymerization of epoxide monomers promoted by tBuP4 phosphazene base: a comparative study of kinetic behavior

Abstract: This contribution fills the need for quantitative mechanistic and kinetic information for epoxide polymerizations catalyzed by tBuP4 phosphazene base.

Cited by 14 publications

References 44 publications

Synthesis of functional and architectural polyethers via the anionic ring-opening polymerization of epoxide monomers using a phosphazene base catalyst

Synthesis of functional and architectural polyethers via the anionic ring-opening polymerization of epoxide monomers using a phosphazene base catalyst

Acetal‐Based Functional Epoxide Monomers: Polymerizations and Applications

Simple/Commercially Available Lewis Acid in Anionic Ring‐Opening Polymerization: Powerful Compounds with Multiple Applications in Macromolecular Engineering

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Product

Resources

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Polymerization of epoxide monomers promoted by tBuP₄ phosphazene base: a comparative study of kinetic behavior