Metal‐free ring‐opening polymerization of glycidyl phenyl ether initiated by tetra‐<i>n</i>‐butylammonium acetate and its application to the hydroxyl‐terminated telechelic polymer

Morinaga, Hisatoyo; Ujihara, Yusuke; Yamanaka, Takahiro; Nagai, Daisuke; Endō, Takeshi

doi:10.1002/pola.24833

Cited by 14 publications

(6 citation statements)

References 20 publications

(41 reference statements)

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“…As a representative example, the average diameter of N1 from AFM (gold substrate, Figure B), DLS (chloroform solution, Figure S1), and TEM (carbon-coated grid, Figure S2) measurements was found to be 36, 35, and 40 nm, respectively. Upon intrachain ROP of the GMA units, − a complete disappearance of the 1 H NMR bands corresponding to glycidylic protons was observed (Figure C). SCNP formation was found to complete after only 3 h of reaction time, pointing to a very fast intrachain ROP process (Figure S3).…”

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confidence: 78%

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Endowing Single-Chain Polymer Nanoparticles with Enzyme-Mimetic Activity

et al. 2013

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ABSTRACT:The development of simple, efficient and robust strategies affording the facile construction of biomimetic organocatalytic nano-objects is currently a subject of great interest. Herein, a new pathway to artificial organocatalysts based on partially collapsed individual soft nano-objects displaying useful and diverse biomimetic catalytic functions is reported. Single-chain polymer nanoparticles endowed with enzyme-mimetic activity synthesized following this new route display: i) a relatively extended morphology under good solvent conditions, as revealed by small angle neutron scattering and coarse-grained molecular dynamics simulation results, ii) multiple, compartmentalized and accessible catalytic sites in which borane catalytic units are retained via B ... O interactions, and iii) unprecedented reductase and polymerase enzyme-mimetic properties.

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confidence: 78%

“…S2) measurements was found to be 36, 35, and 40 nm, respectively. Upon intrachain ROP of the GMA units, [29][30][31][32][33] a complete disappearance of the 1 H NMR bands corresponding to glycidylic protons was observed (Fig. 1C).…”

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confidence: 99%

Endowing Single-Chain Polymer Nanoparticles with Enzyme-Mimetic Activity

et al. 2013

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“…Besides being controlled, efficient, and facile, an ROP system is also expected to meet the rising demand for “green” polymers, especially for PEO which is widely used for biomedicine, pharmaceutics, cosmetics, etc. Organocatalytic polymerization shows the perspective to fulfill such a task because of the inherent character of producing metal-free polymers and the competitive polymerization efficiency and control exhibited by organocatalysts. − So far, strong organobases including tetra- n -butylammonium salts, , phosphazene bases (PBs), − N -heterocyclic carbenes, − and N -heterocyclic olefins , have been used to catalyze/initiate anionic ROP of epoxides. Although the polymerization efficiency is largely improved compared with that obtained from alkali metal alkoxides, elevating temperature is still needed for most systems, which brings difficulties in handling volatile ethylene oxide (EO) under regular conditions.…”

Section: Introductionmentioning

confidence: 99%

High Efficiency Organic Lewis Pair Catalyst for Ring-Opening Polymerization of Epoxides with Chemoselectivity

et al. 2018

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Ring-opening polymerization (ROP) is a versatile approach to well-defined polymers. Achieving both high efficiency and precise control remains a major challenge. We herein report room-temperature living ROP of epoxides catalyzed by combined organobase and triethylborane (Et 3 B) with water or alcohols as initiators. Extremely high catalytic efficiency (turnover frequency up to 6000 h −1 ) is exhibited despite the relatively mild Lewis basicity and acidity, and the catalyst loading can be minimized to 44 ppm. Poly(ethylene oxide) products are noncytotoxic toward a variety of cell lines even without purification. Poly(propylene oxide) with molar mass as high as 210 kg mol −1 and low dispersity (Đ M < 1.1) can be achieved owing to the absence of detrimental transfer reactions. The chemoselectivity allows the catalyst to be readily applied to living ROP of glycidyl ethers, tailored synthesis of diverse functional/block/nonlinear (co)polyether structures, and one-pot one-catalyst synthesis of polyether-based polyurethane. Our study reveals the effective cooperation modes of the Lewis pair and hydroxyl, including the reversible formation of threecomponent initiation/propagation center with appropriate basicity, activation of epoxide by uncomplexed Et 3 B, and fast activity exchange between dormant and active hydroxy species.

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“…Representative organo-catalysts/initiators for the anionic polymerization or related mechanism of epoxides include onium salts [11][12][13], phosphazene bases [14][15][16][17][18], Nheterocyclic carbenes (NHCs) [19][20][21][22] and N-heterocyclic olefins (NHOs) [23,24].…”

Section: Introductionmentioning

confidence: 99%

N-Heterocyclic carbene/Lewis acid-mediated ring-opening polymerization of propylene oxide. Part 2: Toward dihydroxytelechelic polyethers using triethylborane

Song

Zhao

Zhang

et al. 2020

European Polymer Journal

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Propylene oxide (PO) is polymerized by metal-free ring-opening polymerization (ROP) at 25 °C using N-heterocyclic carbenes (NHCs) and triethylborane (Et 3 B) as a bicomponent catalytic system. Poly(propylene oxide)s with predictable molar mass up to 60 000 g.mol -1 and low dispersity (Ð < 1.10) were obtained without the occurrence of undesirable transfer reaction to the monomer. In presence of an alcohol as the initiator, the ROP of PO follows an anionic mechanism assisted by monomer activation improving the efficiency of NHCs for the polymerization of substituted epoxides. Et 3 B is involved both in the formation of a complexed active center and in the activation of PO. Interestingly, dihydroxytelechelic PPOs can be readily synthesized not only using 1,4benzenedimethanol but also water, both serving as difunctional initiators. Block 2 copolyethers are also prepared by PPO chain extension experiments. All (co)polyethers have been thoroughly characterized by 1 H NMR spectroscopy, SEC and MALDI-TOF mass spectrometry as means to elucidate the reaction mechanisms involved in this chemistry.

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Metal‐free ring‐opening polymerization of glycidyl phenyl ether initiated by tetra‐n‐butylammonium acetate and its application to the hydroxyl‐terminated telechelic polymer

Cited by 14 publications

References 20 publications

Endowing Single-Chain Polymer Nanoparticles with Enzyme-Mimetic Activity

Endowing Single-Chain Polymer Nanoparticles with Enzyme-Mimetic Activity

High Efficiency Organic Lewis Pair Catalyst for Ring-Opening Polymerization of Epoxides with Chemoselectivity

N-Heterocyclic carbene/Lewis acid-mediated ring-opening polymerization of propylene oxide. Part 2: Toward dihydroxytelechelic polyethers using triethylborane

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